JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX

The vast use of transition metal catalysts in organic chemistry makes the citation of every individual metal impractical, so there are limited citations of individual metals. Palladium is one exception where individual citations are common, in keeping with the widespread use of that metal. However, in most cases, the term metal catalyst, or catalyst, metal is used as a heading, usually representing transition metals.

A-SE2 mechanism 893 and the steering wheel model acceleration of Diels-Alder reactions 487 151–152 reactions, high pressure A1 mechanism, acetal hydrolysis and universal NMR database 1038 487 155 hydrogen-bonding 1038 A1,3-strain 196 Cahn-Ingold-Prelog system hydrophobic effect 1038 A2 mechanism, acetal hydrolysis 149–152 in water 1038 487 determination 152 ionic liquids 1038 ab initio calculations 36 D/L nomenclature 149 micellular effects 1038 and acidity 346 Kishi’s NMR method 155 microwave irradiation 1038 and antiaromaticity 71 sequence rules 149–152 phosphate 1039 and nonclassical carbocations absolute hardness 64, 359, 361 solid state 1038 427 table 361 ultracentrifuge 1038 norbornyl carbocation 436 absorbents, chiral 168 ultrasound 1038 ab initio studies 248 absorption, and conjugation 317 zeolites 1038 1,2-alkyl shifts in alkyne anions differential, and diastereomers acceleration, Petasis reaction 1349 168 1202 and cubyl carbocation 413 differential, and resolution 169 acenaphthylene, reaction with and SN2 408–409 abstraction, and vinylic DBr 894 cyclopropane ring opening 907 hydrogenation 852 acenaphthylenes 1285 E2 mechanism 1274 benzylic hydrogens, by radicals acenaphthylene, with DBr 894 transition state for radical 852 acenes, hetero see heteroacenes hydrogen abstraction 849 hydrogen atom, photochemical acenes 61, 85 abnormal Beckmann 330 twisted 85 rearrangement 1326, hydrogen, by radicals, rate 848 zigzag 85 1369, 1377 and carbenes 727 acepentalenes, radical ions 265 abnormal Claisen rearrangement by nitrenes 277 acetal formation, and drying 1419 by radicals, ab initio study agents 1101 abrine esters, as catalysts 310 849 azeotropic distillation 1101 absolute aromaticity 39 by radicals, and mechanism 1102 absolute configuration 149 rearrangements 1346 acetaldehyde, and paraldehyde and biochemical methods 153 by radicals, transition state 1259 and circular dichroism 154 848 rational barrier 193 and GC 153 radical, and stereoelectronic acetals, acid catalyzed hydrolysis and glyceraldehyde 148 effects 853 486 and molar rotation 155 COPYRIGHTEDselectivity by radicals 849 MATERIALand enol ethers 1103 and Mosher’s acid 153 stereoselective 851 and Lewis acids 488 and Mosher’s ester 153 of atoms from radicals 263 and microwaves 1103 and NMR 153 radicals, and alkanes 849 and transacetalization 1103 and optical comparison 153 radicals, and alkenes 852 from alcohols and aldehydes optical rotatory dispersion 154 radicals, transition state 845 1101 and specific rotation 155 abstracts 1614 from aldehydes 1102 the SN2 reaction 153 ABX pattern, NMR 155–156 and ketones 1101

March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, Eighth Edition. Michael B. Smith. © 2020 John Wiley & Sons, Inc. Published 2020 by John Wiley & Sons, Inc.

1917 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1918 SUBJECT INDEX

acetals, acid catalyzed hydrolysis acetylenes, electron density map acidic hydrogen atoms, solvents (Continued) 12 1171 and Eosin Y 1102 excited state 319 acidic Lewis ionic liquids 395 photochemistry 1102 triplet 269 acidity see acid strength from alkynes 918 acetylenic sulfoxides, with acidity scales, and alcohols 353 from amides 720 cuprates 962 and amides 353 from Grignard reagents 570 acetylide ion, with alkyl halides and basic solvents 353 from ketones 1102 596 and calorimetric measurements from ortho esters 570, 1103, with epoxides 596 354 1574 with sulfates 596 and carbon acids 353 from oxidation of hydroxy with sulfonate esters 596 and indicators 353 ethers 866 aci form of nitro compounds, and acidity, solvent see solvent acidity hydrolysis 486 tautomerism 102 acidity, amides versus amines 364 and Brønsted coefficient nitro compounds 1099 acidity, and carborane acids 351 487 nitro compounds, and the Nef and carboxylic acids 21 and SN1 mechanisms 486 reaction 1099 and chloromethylation 656 and isotope labeling 486 acid base reactions, and and conformation 368 rate determining step 487 organometallics 732 and cyclopentadiene 64 ketene see ketene acetals acid catalysis, general 356 and electronegativity 365 labeling 486 alkenes with alcohols 917 and entropy 368, 372 N, Se 924 for the Schmidt reaction 1373 and face strain 366 silyl enol see enol silyl acetals acid catalyzed addition of alkenes and five-membered rings 64 silyl ketene 586, 1180 to alkenes 942 and free energy 373 transetherification 496 addition of water to carbonyls and hybridization 368 with allylic silanes 570 1095 and hydrogen bonding 106, 366 with hydride reagents 1574 aldol condensation 1178 and indicators 352 with silyl enol ethers 570 hydration of aldehydes and and ionic liquids 352 with trialkyl phosphites 501 ketones 1096 and ionic strength 373 acetanilide, nitration 632 hydrocarboxylation 984 and IR 352 acetanilides see anilines, acyl hydrocarboxylation of alkenes and Meldrum’s acid 368 acetate, allylic, with keto acids, 982 and organolithium reagents 247 metal catalyzed 887 hydrolysis 383 and periodic table 365 acetate, as a base 340 Knoevenagel reaction 1187 and phenalene 61 acetate, enol see enol acetates reaction with diketones 1103 and proton transfer 350 acetic acid, cis conformation 192 rearrangement of and resonance 365 dimeric 106 hydrazobenzenes 1422 and s character 368 acetic anhydride, and acyl acid derivatives, with amides and solvent 347, 372 fluoroborate 1025 1248 and solvent effects 371 and dehydration of oximes to acid forms 102 and steric effects 366 nitriles 1325 acid solutions, and the tetrahedral and the Hammett reaction and nitration of aromatic mechanism 1090 constant 372 compounds 631 acid strength 238, 340–345 and the medium 370 conjugate addition 979 and solvent 341–345 benzoic acids, and substituents acetoacetamide, enol content 98 crystallographic scale 346 363 acetoacetic esters, and enol definition 340 carboxylic acids 355 content 98 field effects 362 diketones 368 enol 99 Lewis acids 359 diprotic acids, and statistical enol content and solvent 100 mineral acids 346 effects 366 synthesis 577 resonance effects 363 dithianes 1110 acetohydroxamate buffers 1282 acid–base catalysis 355 esters versus ethers 364 acetolysis see solvolysis acid–base equilibrium 339 F strain 366 rates, table 433 acid–base reaction, formation of gas phase 371 acetone, tautomerism, and homoenolates 242 of alcohols 372 bromination 304 and solvents 576 Hammett acidity function 352 acetoxy ketones, from enols 871 free energy 356 hydrocarbon 238 acetoxy sulfides, by Pummerer HCl and acetate 340 -I effect 362 rearrangement 1603 s rate constant 355 inductive and field effects 21 hydrolysis to aldehydes 1603 acid–base, carbanions + proton intrinsic 372 acetoxy ketones, from ketones 249 kinetic 238 871 acid catalysis, alcohol dehydration Lewis acid, and solvents 372 acetoxylation, of alkenes 1025 495 of active methylene compounds acetyl carbocation 230 acid, normal, definition 350 364, 575 acetylene see ethyne acid, sulfuric see sulfuric acid of ketones or aldehydes 1110 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1919

of PCC 1448 sulfonyl, reduction with metals alkylation 575 of protons, and solvent acidity 1270 and the Knoevenagel reaction 352 acids, superacids 225, 229–230, 1187 of solvents 352 346–347, 698 arylation 575, 819–820 phenols 355 and alkenes 724 and radicals 820 pKa of acid types 341–345 and arenium ions 611 enantioselective 820 protons α- to a heteroatom and benzenonium ions 611 structural variations 820 590 and carbocations 226–227, as nucleophiles 566 solvent 355 410, 439, 1345, 1398 conversion to diazo compounds spectrophotometric and diazonium salts 467 712 measurement 352 and hydration of alkynes 914 functional groups 575 statistical effects 366 ionization 414 with acyl halides 1252 substituent effects 362 and nonclassical carbocations with aryldiazonium salts 710 thermodynamic 238 435 with tosyl azides 712 acids see Brønsted-Lowry acids, and oxocarbenium ions 1381 activity, of radicals 856 Lewis acids, solvent acidity cleavage of alkanes 759 acyals, from anhydrides 1104 acids, amino see amino acids coupling of alkenes 724 acyclic compounds, conformation acids, Brønsted-Lowry see sulfur dioxide 226 188 Brønsted-Lowry acids acids, table, delocalization 753 acyclic molecules, and entropy acids, carboxylic see carboxylic type, table of pKa 341–345 284 acids very weak acids 346 acyl addition see addition acids, fatty see fatty acids acoustic cavitation see cavitation acyl addition intramolecular 981 acids, glycidic see glycidic acoustic cavitation, and Grignard reagents 1129 acids, Lewis see Lewis acid sonochemistry 331 organolithium reagents 1129 acids, sulfinic see sulfonic acids acridinium photooxidant 920 syn or anti 1088 acids, sulfonic see sulfonic acids acrolein, canonical forms 47 water 1095 acids, acid strength 341–345 acrylic acids, from with nucleophiles 1087 activity of proton 352 tosylhydrazones 1161 acylals, and silanes 1105 and hydrogen exchange, actinometer, and photochemical formation of, reagents 1104 electrophilic aromatic mechanism 331 formation, and microwaves substitution 630 activated aromatic rings, and 1104 and keto-enol tautomerism 701 Friedel-Crafts acylation from aldehydes 1104 and pKa 340–347 659 from alkynes 920 aromatic, decarboxylation 755 activated complex 285 metal salts 1104 aryl, decarboxylation 752 activating groups, and acylamidation, of alkenes 1025 as proton donor 339 Friedel-Crafts alkylation acyl anion equivalents 1189 Brønsted, addition of thiols to 649 and Knoevenagel reaction 1189 alkenes 922 and multiple substituents 621 acylation, and substitution 403 carbon 346 for aromatic substitution 776 C- and O- 722 and acidity scales 353 in aromatic compounds 614 dithianes 1256 in liquid ammonia 347 in SNAr reactions 776 enol, C- and O-acylation 722 catalysts, addition of water to activation energy, aldol-type Friedel-Crafts 641, 658–663 alkenes 912 reactions 1174 Shvo’s catalyst 1250 conjugate 339 and Bell–Evans–Polanyi of alcohols 1233 conjugated, decarboxylation principle 620 of alkenes 719, 981, 1005 755 arenium ions 614 of amides 1248 hard, definition 359 Arrhenius 303 of amines 1240 hardness 359 carbene to alkenes 1068 and Merrifield synthesis inorganic, esters, hydrolysis activation, enthalpy 285, 333 1244 485 activation, free energy 285 and microwaves 1240 with anhydrides 1236 activation hardness 625–626 and ultrasound 1240 IUPAC terminology 339 and electrophilic aromatic ionic liquids 1241 Lewis, addition of thiols to substitution 625 microwaves 1241 alkenes 922 activation strain model 283 polymer-bound 1241 proton-transfer reaction 350 activation volume, and Weinreb amides 1505 protonation of carbanions 237 E1-E2-E1cB Spectrum of conjugated compounds 979 reaction with alkenes 894 1287 of dienes 720 soft, definition 359 and high pressure 390 of enamines 587 softness 359 and reactivity 390 of ketones 1253 strength 340 activation-strain model, E2 and regioselectivity 1253 and structure 361 SN2 1292 with nitriles 672 strong, stability of carbocations active methylene compounds, acyl azides 532 225 acidity 364, 575 acyl carbocations 230 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1920 SUBJECT INDEX

acyl carbon, substitution reactions adamantanes, and chirality 140 aerobic oxidation 1457 452 and strain 212 allylic and benzylic acyl compounds, addition to carbocations 233–234, 1340 hydrocarbons 1480 alkenes or alkynes 981 substrates, carbocations 451 aggregates, and dialkylamide acyl cyanides, from esters and addition compounds 114, 116 bases 369 nitriles 1256 addition reactions, carbenes 272 and enolate anions 370 acyl halides see halides IUPAC nomenclature 398 and HMPA 369 acyl hydrazide 552 to cyclopropanes 906 dianion 370 acyl radicals 842, 890 mechanism 907 mixed, organolithium reagents acyl substitution, reactivity of radical 907 548 substrates 1093 addition, anti see anti of organolithium reagents 245, acylcarbenes 274 conjugate see conjugate 750, 1134 acylcyanation, of imines 1213 addition aggregation, ab initio, enolate acylimidazoles 1234 addition, [1,3]-dipolar see anions 248 acylindoles 663 [3+2]-cycloaddition and organolithium reagents acylium ions 230, 661 addition–elimination mechanism 247 Friedel-Crafts acylation 659 see mechanism ion, of organolithium reagents with alkenes 720 addition, syn see syn 1162 with nitriles and alkenes 1026 addition, 1,2 versus 1,4 898 phenyllithium 248 acyloin condensation 1598 1,3-dipolar, alkyl azides 1022 aggregation state, enolate anions and chlorotrimethylsilane 1598 acyl 1087 248 and Dieckmann condensation and I strain 380 organolithium reagents 247 1599 and reactivity 380 tert-butyllithium, solvent and surface area of metal 1599 and strain 380 effects 245 and surface reaction at sodium decarboxylative 887 organocuprates 961 1599 [1,3]-dipolar 1027–1035 AIBN (azobiisobutyronitrile) 840 and triazolium precatalysts electrophilic 281, 892 and radical conjugate addition 1598 and stereochemistry 892 969 and ultrasound 1598 and the SN1 mechanism 892 and radical cyclization 971, catenanes 1598 cyclic intermediates 893 974 crossed 1598 mechanism 890 and radical halogenation 863 importance of K in Na 1599 simultaneous addition 893 and radicals 862 mechanism 1599 termolecular addition 893 and the Schmidt reaction 1374 procedures 1598 free radical 281, 896 conjugated acids with nitric structural features 1598 HX to alkynes 911 acid 874 with trimethylsilyl chloride nucleophilic 281 coupling alkanes and alkynes 1599 and carbonyls 1088 598 acyloins 1189 See also hydroxy and the tetrahedral decomposition to radicals 841 ketones mechanism 1088 formation of radicals 841 and the benzoin condensation pericyclic 281 halides with oximes 1217 1216 radical, with alkenes 263, 852 lactone formation 604 by the acyloin ester simultaneous 281 NBS, amines and aldehydes condensation 1598 termolecular, mechanism 893 872 reductive coupling of esters to alkenes 281 vinyl carboxylic acids and nitric 1598 and steric hindrance 904 acid 874 trapping with trimethylsilyl and strain 379 air, with thioketones 1109 chloride 1599 nitrenes 277 aziridines, from hydrazines and acyloxy ketones 1025 to conjugated systems 898 akenes 1022 acyloxy radicals 263 to cyclopropanes, AIST 1621 acyloxylation 870 Markovnikov’s rule 906 alanes 526 and Markovnikov’s rule 1025 regioselectivity 906 reducing agents 1540 of alkenes 1025 AdE2, electrophilic addition, reduction of aldehydes or of alkynes 1026 bimolecular mechanism ketones 1540 of enols 871 892 reduction of enamines 1585 of ketones 871 AdE3 mechanism 895 vinyl, from alkynes 938 radical 871–872 adipic acid, from cyclohexanone alanine 148 with metal acetates 871 1465 alcohol dehydration, and acylthiazolidinethiones, chiral adsorption, alkenes on a metal supercritical carbon 1184 1517 dioxide 392 AD-mix-α, and asymmetric aerobic dehydrogenative alcohol dehydrogenase, and dihydroxylation 1009 aromatization, transamination 521 AD-mix-β, and asymmetric cyclohexanone imines alcohol–alkynes, and hydrogen dihydroxylation 1009 1444 bonding 112 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1921

alcohols, acid catalyzed addition and the Williamson ether to cyclic ethers 866 to nitriles 1106, 1257 synthesis 490 to esters 606 acylation 1227, 1233 and transesterification 1232 to Grignard reagents 568 addition to aldehydes or transetherification 496 to isonitriles 527 ketones 1101 anti-Markovnikov, via to nitriles 600 to alkenes 980 hydroboration 1385 alcohols, coupling 568–569 to carbonyls 1101 azido 523 with alkyl silanes 547 to isocyanates 1105 benzylic, and atropisomers 143 with Grignard reagents 568 alkyl azides, and Mitsunobu oxidation with Mn(OAc)3 with organometallics 568 reaction 1374 1450 metal catalyzed 568 alkynyl, conversion to dienes oxidation with MnO2 1450 with organolithium reagents 1300 alcohols, by anti-Markovnikov 569 alcohols, allylic, and asymmetric addition to alkenes 913 alcohols, Cr(VI) oxidation, epoxidation 1017 by Cannizzaro reaction 1600 kinetics 1449 and Sharpless asymmetric by enantioselective mechanism 1449 epoxidation 1017 hydroboration 935 alcohols, cyclic, from dienes and and the Baylis-Hillman reaction by hydrolysis of borates 1539 trienes 1385–1386 1149 by Meerwein-Ponndorf-Verley cycloalkyl, from cycloalkyl by allylic oxidation Sharpless reduction 1538 amines and nitrous acid method 1482 by oxidation of 1356 by allylic oxidation with bora-1,3-dioxolanes 1385 cyclobutyl, from selenium dioxide 1481 by oxidation of boranes 1385 cyclopropylcarbinyl by oxidation of alkenes 1477 by oxidation of hydrocarbons amines 1356 by reduction of conjugated 1475 cyclopropyl propargylic, carbonyls 1533 by oxidation of hydrocarbons, rearrangement 1357 by the Prins reaction 1213 enantioselectivity 1476 cyclopropylcarbinyl, from from allylic sulfones 1422 by oxidation of hydrocarbons, cyclobutyl amines 1356 from epoxides 1302 reagents 1476 FVP 1407 isomerization with metal by oxymercuration 913 alcohols, dehydration 495 catalysts 1367 by reduction of aldehydes or acid catalyzed 1299 oxidation 1448 ketones 1532 and carbocations 495 to enones 1482 by reduction of amides 1581 and Hofmann’s rule 1299 with chromium reagents by reduction of boranes 1387 and Mitsunobu reaction 495 1448 by reduction of carboxylic acids and Zaitsev’s rule 1299 with Mn(OAc)3 1450 1546 dehydrating agents 1299 with MnO2 1450 by reduction of carboxylic in supercritical carbon dioxide metal catalyzed 1449 esters 1537 392 rearrangement with PCC 1448 by reduction of carboxylic mechanism 1300 with potassium permanganate esters, microwaves 1548 with metal catalysts 1300 1450 by reduction of carboxylic alcohols, deoxygenation 1574 with Re catalyst 1367 esters, reagents 1547 diene, rearrangement 1405 alcohols, and acidity scales 353 by reduction of epoxides, epoxy 1135 and boron-to-carbon reagents 1531 rearrangement 1356 rearrangement 1385 by Tamao-Fleming oxidation alcohols, formation of enol ethers and carbonylation of alkyl 499 496 halides 604 by the Barbier reaction 1130 alcohols, from aldehydes 1146 and carbonylation of amines by the Bouveault-Blanc from aldehydes or ketones 765 procedure 1537 1129 and carbonylation of aryl alcohols, carbonylation 604 from alkenes 912, 1385 halides 821 carbonylation with alkyl halides from alkylboronic acids 735 and formation of carbocations to give esters 604 from amides 1549 226 chiral, from chiral alkyl halides from amines 505 and Friedel-Crafts alkylation 539 from boranes 1387 649 via hydroboration 935 and carbon monoxide and Koch-Haaf reaction 604 chromium(VI) oxidation, 1386–1387 and Schotten-Baumann mechanism 1449 mechanism 736 procedure 1227 conjugate addition 977 from carboxylic acids 1546 and Swern oxidation 1451 alcohols, conversion to alkyl metal catalysts 1546–1547 and the Koch-Haaf reaction fluorides 539 Bouveault-Blanc procedure 982 to alkyl halides 536, 538 1548 the Pinner synthesis 1106 in ionic liquids 538 from diazoketones 485 and the Ritter reaction 1257 to amides 1257, 1494 from epoxides 571, 1531 and the SNi mechanism 441 to azides 531 from esters 1548 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1922 SUBJECT INDEX

alcohols, from aldehydes with alternative hypervalent reaction with aldehydes or (Continued) iodine reagents 1454 ketones, compatible from esters and organometallics with Bobbitt’s reagent, functional groups 1102 1157 chemoselectivity 1453 reaction with phosgene 1106 from ethers 540 with Collins reagent 1448 reaction with thiols 508 by Wittig rearrangement with Cr(VI), ionic liquids 1447 reagents utilized with DMSO, 1384 over oxidation 1448 for oxidation 1451 from Grignard reactions 571, phase transfer 1447 reduction of acyl halides 1580 1129 with Dess-Martin periodinane reduction, reagents 1571 from halomethyl ethers 1386 1453 reductive alkylation of from hydrocarbons and ozone with dichromate 1447 aldehydes 1104 1476 with DMSO and DCC 1451 solvent free oxidation 1448 by oxygen insertion 1477 and oxalyl chloride 1451 solvolysis 378, 1342 by oxygen insertion, reagents 1451 structural variation of chromates mechanism 1477 with hypervalent iodine 1453 for oxidation 1448 from inorganic esters 485 with Jones reagent 1447 TEMPO oxidation, in ionic from organolithium reagents with manganese dioxide 1450 liquids 1452 571 with potassium permanganate solvent free 1452 from peroxides 1576 1450 thermodynamic kinetic from trifluoroborates 1387 with TEMPO, co-reagents asymmetric amination 517 alcohols, gas phase acidity 372 1452 thiocyanate, ammonium, and green resolution 171 with TPAP 1454 Mukaiyama reagent 533 Grignard reagents, with and Burgess reagent 1451 vinyl 99 aldehydes or ketones 1129 and Cr(IV) 1449 vinylcyclopropyl, sigmatropic halo, with LiAlH4-TiCl43 1321 and DDQ 1456 shifts 1404 halogenation 536 and electrochemistry 1456, alcohols, with acyl halides 1227 and ionic liquids 537–538 1458 with acyl halides and Zn 1227 rearrangement 539 and Grubbs’ catalyst 1458 metal catalysts 1227 homoallylic 1214 and microwaves 1458 SN1 mechanism 1227 aldehydes 1209 and nanoparticles 1458 SN2 mechanism 1226 pyrolysis 1328 and phase transfer 1450 tetrahedral mechanism 1227 hydride reagents 1571 and ultrasound 1456 with aldehydes 1105 hydrogenolysis 1571 Fe/9-azabicyclo[3.3.1]nonan-N- with alkenes 916 in esterification reactions 1229 oxyl 1452 and hydrazoic acid 1374 insertion reactions 729 in ionic liquids 394, 1457 base catalyzed 919 intramolecular addition of monoperoxysulfate 1456 enantioselectivity 917 alkenes 918 Oxone 1458 formation of metal catalyzed dehydration with hydrogen peroxide 1455 tetrahydrofurans 918 1300 with metals 1455–1458 Markovnikov’s rule 916 oxidation with TEMPO 1452 with miscellaneous reagents metal catalysts 917 Moffatt oxidation 1451 1455–1458 photochemical 919 nitroxyl radical oxidation 1452 with oxoammonium salts regioselectivity 916 Oppenauer oxidation 1450 1453 with silanes 917 organolithium reagents, with alcohols, oxidizing reagents for with anhydrides 1227 aldehydes or ketones 1129 making cyclic ethers 866 catalysts 1228 organometallics with aldehydes permanganate oxidation, and metal catalysts 1228 or ketones 1136 ultrasound 1450 microwave irradiation 1228 alcohols, oxidation, by catalytic photochemistry 317 with aziridines 498 dehydrogenation 1454 photooxidation 1456 and Montmorillonite clay carboxylic acids, and propargyl, acid catalyzed 574 oxammonium salt 1492 rearrangement 1368 with boronic acids 595 in supercritical carbon dioxide base induced rearrangement with carbon disulfide 1106 1448 1368 alcohols, with carboxylic acids to aldehydes 866 coupling with alkynes 876 1229 to aldehydes or ketones 1447 isomerization with metal acid catalyzed 1228 to carboxylic acids 866, 1492 catalysts 1368 catalysts 1229 to carboxylic acids, and Meyer-Schuster cyclization 1230 microwaves 1492 rearrangement 1367 dehydrating agents 1231 to carboxylic acids, and with hydrazines 701 equilibrium 1229 TEMPO 1492 alcohols, protection as ethers 492 ionic liquids 1229 to carboxylic acids, reagents for protonolysis and carbocation lactones 1230 1492–1493 formation 235 mechanism 1231 to cyclic ethers 866 rates of solvolysis 378 metal catalyzed 1229 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1923

Mitsunobu reaction 1230 aldehydes, aliphatic Vilsmeier aldehydes, by acid treatment of solid state 1229 reaction 720 Reissert compounds 1552 water soluble carbodiimides alkylation 579 by base cleavage of acyl 1231 amphiprotic properties 701 sulfonylhydrazides 1552 XtalFluor-E 1230 and autoxidation 867 by Dibal reduction of esters alcohols, with carbon disulfide and bisulfite addition product 1551 1107 1111 by DMSO-type oxidation of with DAST 539 and carbanions 250 alcohols 1451 with diazomethane 494 and Claisen condensation by hydrolysis of C=N with epoxides 496 1183 compounds 1096 with halogens 997 and Collman’s reagent 602 by hydrolysis of imines 1491 with halogens and alkenes 996 and hemiaminals 1111 by hydrolysis of Schiff bases with HBr or HI 540 and hydrogenolysis 1577 1097 with hydrazoic acid 1374 and McMurry reaction 1597 by McFadden-Sevens reduction with hydrogen sulfide 506 and Peterson alkenylation 1552 with inorganic acids 504 1191 by Oppenauer oxidation 1450 with isocyanates, mechanism and Piers hydrosilation 1541 by oxidation of alcohols 866, 1105 and reagents for hydrolysis of 1447 with isothiocyanates 1105 C=N compounds 1097 by oxidation of alkenes, with ketenes 919, 1364 and tautomerism 97 reagents for 1499 with ketones 584 and the Barbier reaction 1136 by oxidation of alkyl halides alkylation 584 and the Baylis-Hillman reaction 1489 with Lawesson’s reagent 506 1149 by oxidation of amines 1491 with lead tetraacetate 866 organocatalyst 1150 by oxidative cleavage of diols with mineral acids 537 protein catalyzed 1150 1463 with NaOH and carbon and the benzoin condensation by ozonolysis of alkenes 1466 disulfide 1304 1216 by pyrolysis of allylic ethers with onium salts 498 and the Cannizzaro reaction 1329 with organotitanium reagents 1601 by pyrolysis of homoallylic 569 and the Knoevenagel reaction alcohols 1328 with polymer supported 1187 by reduction of acyl halides, oxidizing agents 1449 and the Mannich reaction 1123 reagents 1549 with sulfonamides 1268 and the Perkin reaction 1190 by reduction of anhydrides with sulfonyl halides 1268 and the Reformatsky reaction 1551 with thiols and microwaves 507 1152 of boranes 1387 with thionyl chloride 441, 537 and the Stetter reaction 981 of carboxylic acids, reagents with trifluoroborates 494 and the Tischenko reaction 1550–1551 alcoholysis, of amides 1234 1602 of carboxylic esters, reagents of anhydrides, and Tollens’ reaction 1193 1550–1551 enantioselectivity 1228 and Umpolung 589 of esters 1551 of nitriles 1106 aldehydes, aryl, and reverse of esters, reagents 1551 aldehyde–alkenes, with Gatterman-Koch reaction of imidazoles 1552 organometallics 1143 683 of nitriles, reagents 1558 aldehyde–alkynes, with benzoin condensation 1216 aldehydes, by Rosenmund organometallics 1143 by benzylic CH oxidation 1478 reduction 1549 aldehyde–carboxylic acid anions, by α-CH oxidation of methyl by Stephen reduction 1558 intramolecular 1184 aromatic compounds 1478 by the Barton reaction 1434 with amines 1184 decarbonylation 683 by the Etard´ reaction 1478 aldehydes, alkylation 580 Duff reaction 666 by the Kornblum reaction 1490 acetal formation 1101 formation of hydrazones 1115 by the Kronke¨ reaction with acid catalyzed addition of Gatterman-Koch reaction 666 benzylic halides 1491 aldehydes 1259 reagents, for allylic and benzylic by the Meyers’ reaction 591 acid catalyzed rearrangement oxidation 1478–1480 by the Nef reaction 1098 1359 Reimer-Tiemann reaction 666 by the Sommelet reaction 1490 acidity of α-hydrogen 1110 via Friedel-Crafts formylation by the Sonn-Muller¨ method aldehydes, addition of alcohols 665 1553 1101 with ammonia and metal by the Wacker process 1499 of allylic boranes 1145 peroxides 872 by Vilsmeier-Haack reaction enantioselectivity 1145 with carbon monoxide and 663 of amides 1122 hydrogen 666 aldehydes, catalytic of diazomethane 1365 aldehydes, azine formation 1116 hydrogenation 1536 of water 1095 base induced deprotonation 703 chemoselective reducing agents to alkenes 981 borane reduction reagents 1539 1533 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1924 SUBJECT INDEX

aldehydes, catalytic hydrogenation from enol borinates 967 aldehydes, reductive alkylation (Continued) from enols 753 with alcohols 1104 condensation with esters 1183 from formic acid and Grignard reductive amination 1118 conjugate addition, and reagents 743 reductive coupling to diols, microwaves 979 from glycidic acids 752–753 reagents 1593 aldehydes, conjugated see Grignard reagents 821 relative reactivity, steric effects conjugated aldehydes from halo amides 1370 1089 and conjugate addition 956 from homoallylic alcohols steric hindrance and reduction and metathesis 1430 1328 1533 Michael addition with from ketones 1195 structural variations and the organolithium reagents from metalated imines 1266 Wittig reactions 1196 963 from nitriles 1557 tautomerism and sugars 103 with boranes 967 from nitro compounds 1492 trimerization 1259 aldehydes, conversion to acetals from organolithium reagents aldehydes, with active hydrogen 1102 821 compounds 1169 to acyl chlorides 862 from organometallics 743 with acylperoxides 871 to acyl radical 842 from vinylic compounds 485 with alcohols 1105 to amides, flow reactions from Weinreb amides 1552 esterification, metal catalyst 1498 halogenation, enantioselectivity 1497 to amino alcohols 1595 704 esterification, reagents 1497 to diamines 1595 aldehydes, Henry reaction 1185 with aldehydes 1259 to enol thioether 1109 heteroaryl, Reimer-Tiemann with alkenes, metal catalyzed to gem-difluoro compounds reaction 666 981 1128 homologation 1365 photochemical 981 to homoallylic alcohols 1209 hydration 1095 with alkyne anions 1143 to keto esters 722 hydride reduction, mechanism enantioselectivity 1144 to ketones 722 1535 metal catalyzed 1143 to nitriles 601, 1497 hydrogenation, ionic liquids with allylic silanes, and to sulfides 1110 1543 transition metals 1148 to thioamides 1498 hydrolysis of acetoxy sulfides with allylsilanes 1148, 1209 aldehydes, coordination with 1603 metal catalyzed 1148 SnCl4 368 iodination 705 with allyltrichlorosilane 1149 coupling to form akenes 1597 iodine, and ammonia 873 with amide bases 1172 coupling to give carboxylic isotopic exchange 703 with amides 1184 esters, reagents 1602 Lewis acid catalyzed addition of with amines 1111, 1118 cyclization 981 allylic silanes 1148 and alkyl halides 1120 decarbonylation 327, 1346 mechanism of hydration 1096 and hydrogen 1118 with Wilkinson’s catalyst Meerwein-Ponndorf-Verley metal catalyzed 1112 889 reduction 1538 with anhydrides 1190 dehydrogenation 1446 metal catalyzed with aziridines 498 deoxygenation 1577 decarbonylation 888 with boranes 1146 Diels-Alder reaction 1053 mechanism 889 enantioselectivity 1146 enol content 98 metal mediated addition of metal catalyzed 1146 enolate anions 584 haloesters 1152 with boronic acids, metal enzymatic reductions 1541 more reactive than ketones catalyzed 1146 fluorination 705 1089 with boronic esters, metal formation of enolate anion aldehydes, oxidation to amides, catalyzed 1147 1172 NHC catalyst 1498 with carbanion named reactions, formation of hydrates 1095 to carboxylic acids 1494–1495 table 1170 formation of nitriles, reagents aldehydes, reduction with boranes with conjugated compounds for 1118 1539 1149 formation of oxocarbenium with enzymes 1543 with conjugated ketones, and ions 1360 with hydrides 1532 radicals 1217 aldehydes, from alkyl halides with metals 1537 with cyanide 980 601, 604 with silanes 1541 and conjugate addition 979 from allylic ethers 1384 with sodium in ethanol 1537 with diazoalkanes 1206 from amides 1552 mechanism 1537 with enolate anions 248 from boranes 1387 with tin hydrides 1540 with esters 1183 from boronic acids 1387 biocatalyst 1542 with Grignard reagents 11129 from carboxylic acids 1474 hydrogen transfer 1541 with halo esters 1190 from chloroiminium salts Luche reagent 1533 with HCN 1210 1558 Luche reduction 1533 biocatalysts 1210 from dihalides 484 metal hydrides 1533 organocatalysts 1210 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1925

aldehydes, with hydrazines and Claisen-Schmidt reaction with preformed enols 1178 1115–1116 1173–1174 Zimmerman-Traxler model with hydroxylamine 1115 and dehydration of alcohols 1176 and formic acid 1117 1299 aldol reaction see aldol with isocyanides and carboxylic and dihalides 484 condensation acids 1265 and enolate anions 580 aldol-like reaction, enol borates with ketenes 1260 and enols 1178 1184 with ketones 1193 and Hunig’s¨ base 1174 aldol-Robinson cascade reaction aldol condensation 1173 and hydroformylation 989 1179 with lithio-silanes 1191 and Ivanov condensation 1176 aldol-type condensation, with methoxyvinyllithium 1189 and LDA 1173 thioesters 1183 with nitro compounds 1185 and organocatalyst 310 aldol-type reactions 1171 with Nozaki-Hiyama reaction and oxocarbenium ions 1178 activation energy 1174 1141 and pKa 1173 computational study 1174 with organoaluminium and SET mechanism 1171 aldols, and atropisomers 143 compounds 1139 and Soxhlet extractor 1173 aldoximine, heating 1376 with organochromium and the Cannizzaro reaction Aldrich Library of Spectra 1622 compounds 1141 1601 algorithm, dielectric screening enantioselectivity 1141 and Tischenko reaction 1602 effects 469 with organocuprates 1143 and Zimmerman-Traxler model alkali fusion, and preparation of with organolithium reagents 1176 phenols 781 1129 aldol condensation, anti- 1184 alkaloids, atropisomers 143 with organometallics 166, aqueous 1177 demethylation 1592 1136 biocatalytic 1177 alkane–hydrogen exchange 1519 elimination 1136 chiral ligands 1178–1179 alkanes, addition to alkenes 940 enantioselectivity 1137 cross-coupling, aldehydes and addition to alkenes, and intramolecular 1143 ketones 1173 Friedel-Crafts reactions metals used 1136–1142 deep eutectic solvents 1177 939 selectivity 1138 diastereoselectivity 1175 amination 526 aldehydes, with organotitanium directed 1178 and bond angle 27 compounds 1140 enantioselective 1176–1178 and conformations 191 with organozinc compounds enzyme mediated 1172 and guest–host interactions 123 1140 equilibrium conditions 1179 and nitric acid 711 enantioselectivity 1140 formation of stereoisomers and radicals 711 with other organometallic 1175 and photochemistry 317 compounds 1143 homo-coupling, aldehydes and and photosensitization 874 with phenylhydrazine 1419 ketones 1172 and superacids 724 with phosphorus ylids 1194 intramolecular 214, 1178 alkanes, by addition of alkanes to with potassium cyanide 1216 intramolecular, and entropy alkenes 939 with propargyl substrates 1145 1178 by coupling of alkanes 874 with silyl enol ethers, with ionic liquids 1177 by decyanation of nitriles 760 chiral boranes 1182 kinetic conditions 1174 by hydrogenation of thioethers with sodium azide 1250 mechanism 1172 883 with sodium bisulfite 1111 mixed, and the Tollens’ reaction by radical addition to alkenes with sulfonamides 1122 1193 970 with sulfur ylids 1204 Mukaiyama 1180 by reductive cleavage of with the Nysted reagent 1203 metal catalysts 1181 cyclopropanes 1530 with thiols 1108 nitroso 1180 alkanes, carbocation formation with TMSCN, solvent free organocatalysts 1177 226 1210 products 1172 chlorination, selectivity 859 with transition metals, and acyl aldol condensation, cleavage by hydrogenation 759 radicals 842 regioselectivity 1174 with superacids 759 with trifluoroborates, Pd retro 751 and steric factors 759 catalyzed 1147 selectivity 1174 mechanism 759 with vinyl acetate 1366 side reactions 579–580 alkanes, conversion to amides 873 with ylids 1193 solvent free 395, 1178 coupling alcohols with Wolff-Kishner reduction 1577 solvent free carboxylcoumarins organometallics 568 aldol see homoaldol 395 coupling with carbocations 724 aldol condensation 756, 1171 stereoselectivity 1175 cyanation 723 catalyst 1178 thermodynamic conditions cyclic, oxidation to ketones aldehyde with ketone 1173 1179 1477 and asymmetric synthesis 166 transition state 1176 perdeuteration 698 and chiral auxiliaries 1177 vinylogous 1178 dehydrogenation 1446 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1926 SUBJECT INDEX

alkanes, conversion to amides metal catalysts 1426 of haloamines 1000 (Continued) reaction conditions 1429 in ionic liquids 1001 diazotates, conversion to reactivity 1429 of haloazide 1002 azoxyalkanes 533 reactivity of alkenes 1429 of HBr, with peroxides 970 dications 233 recyclable catalysts 1429 of HCN, and phase transfer 991 formation of carbocations 526 selectivity 1428 of hydrogen sulfide 922 alkanes, from aldehydes 888–889 stereoretentive 1429 of iodine azide 1002 from alkenes 1513 supercritical carbon dioxide of iodo azide, mechanism 1002 from alkyl halides 555, 1568 1429 of isothiocyanates 1000 from epoxides 1531 synthetic importance 1428 of nitrenes 277 from esters 1574 (Z)-selective 1428 of nitryl chloride 1001 reagents 1575 alkene reactivity, alkene of nucleophiles 895 from organocuprates 555 metathesis 1429 of organometallics compounds alkanes, halogenation 857 and molecular electrostatic 948 halogenation, and UV 857 potentials 903 of polyhalo compounds 1004 heat of atomization 29 and steric hindrance 902 of radicals 263, 970 hydrogen abstraction by regioselectivity 902 of sulfonic acids 921 radicals 849 alkene–acids, cyclization 1026 of sulfonyl halides 999 hydrogenation of thiols 883 alkene–aldehydes, with of thiols 922 hydrogenolysis 1444 organometallics 1143 alkenes, addition reactions 281 metal catalyzed addition to alkene–amines, cyclization 926 addition to carbocations 236 alkenes 940 formation of cyclic amines 515 addition, and steric hindrance nitration 711 alkene–carboxylic acids, and 904 organometallics with alkyl halolactamization 998 adsorption on a metal 1517 halides 558–563 and iodolactonization 998 alcohols and alkoxy-amination oxidation with Chloramine-T halogenation 998 1020 1477 alkene–metal complex 1517 alkoxy carbonylation 984 with nanocrystalline cobalt alkenes, α,β-versusβ,γ-double allylic oxidation with selenium oxide 1477 bond preference 909 dioxide, mechanism 1482 photobromination 857 acceptor molecules 116 amidation 930 radical coupling 874 acid catalyzed addition of amidation, enantioselectivity removal of hydride ions 698 alkenes 942 930 trialkyl, metal catalyzed addition of formaldehyde amidation, intramolecular 930 addition to alkynes 951 1213 amidation, metal catalyzed 930 via alkylborane coupling 882 dehydration of alcohols 1299 alkenes, amination 713, 924 via coupling reactions 724 acylamidation 1025 amino-carbonylation 984 with Lewis acids 1353 acylation 719, 981 aminomercuration 1020 with radicals 849 acyloxylation 1025 aminosulfenylation 1024 Wurtz reaction 549 with palladium acetate 871 alkenes, and allylic carbocations alkene addition, and acyloxymercuration– 228 hyperconjugation 906 demercuration and anisotropy 56 electronic effects 905 920 and Birch reduction 1520, 1525 electrophilic, mechanism 903 alkenes, addition of acyl and Bredt’s rule 1288 alkene–aldehydes, by [2,3]-Wittig compounds 981 and bromonium ions 897 rearrangement 1422 of alcohols 980 and carbene rearrangements alkene–amides, cyclization 1027 of aldehydes 981 1349 alkene metathesis 1424 of aldehydes, photochemical and carbene transfer 1068 alkene reactivity 1429 981 and complex formation 116 and chain metathesis 1426 of alkanes 939 and E/Z nomenclature 176 and Grubbs catalysts 1427 of alkanes, in ionic liquids 939 and electron donating and the Shrock catalyst 1427 of alkyl halides 1003 substituents 899 aqueous micellar medium 1428 of alkyl halides, Friedel-Crafts and electron withdrawing artificial metalloenzyme 1428 catalysts 1003 substituents 899 compatible functional groups of alkyl halides, metal and far UV-spectra 901 1428 catalyzed 1004 and formation of bis(selenenyl) cross metathesis 1426 of amines 980, 1021 compounds 1018 diynes 1430 of anions 249 and Friedel-Crafts alkylation enantioselectivity 1428 of azido groups 1021 648, 651 equilibrium 1425 of carbamates 931 and hydroboration 932–937 formation of cyclic dienes 1430 of carbenes 267, 272, 1067 and hydrozirconation 938 formation of lactones 1430 of carbenoids 1067 and Julia-Colonna epoxidation, ionic liquids 1429 of carboxylic esters 980 enantioselectivity 1016 mechanism 1425 of Grignard reagents 938 and kinetic resolution 171 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1927

and metal catalyzed diazoalkane by coupling of aldehydes and to ketones 1500 reactions 1068 ketones 1597 to lactones 920 and neighboring groups 427 by decarboxylation of amides to phosphine oxides 929 and NMR 55 1304 to phosphonate esters 929 and peroxides 910 by decarboxylation of esters alkenes, coupling, metal catalysts and PES 15 1303 945 and ring current 55 solvent free 1304 to alkenes, metal catalyzed and Sharpless asymmetric by decomposition of inorganic 945 dihydroxylation 1008 esters 1305 with halocarbonyl compounds and the Baeyer test 1006 by dehydrogenation 1446 801 and the ene reaction 952 by deoxygenation of diols 1315 alkenes, crowded, and strain 220 and the Heck reaction 810 by desulfurization of alkenes, cyclic, and Bredt’s rule and the Koch reaction 982 thiophenes 884 217 and the Koch-Haaf reaction by elimination of dihalides, by McMurry coupling 1597 982 reagents for 1319 by the Story synthesis 1332 and the Prins reaction 1213 of hydroxy acids 1323 from dialdehydes 1597 and the Stetter reaction 981 by Hofmann elimination 1305 oxidative cleavage 1470 and thiourea, metal catalyzed by hydroboration of alkynes ozonolysis 1467 formation of thiiranes 1522 alkenes, cyclization with 1018 by metal catalyzed dehydration organolithium reagents and triflamides, cyclization 931 of alcohols 1300 947 and Woodward modification of by oxidation coupling of alkyl cycloaddition to alkenes the Prevost reaction 1007 halides 1508 1056–1067 and X-ray crystallography 220 by Peterson alkenylation 1191 cycloaddition with dienes animation, and temperature by pyrolysis of allylic ethers 1035–1055 effects 924 1329 cyclopropanation 1070 alkenes, anti-dihydroxylation of homoallylic alcohols 1328 synergistic effect 1071 1007 of sulfones 1310 dehydrohalogenation 1311 anti-Markovnikov addition of of sulfoxides 1310 mechanism 1312 radicals 970 of β-lactones 1323 suitable bases 1311 hydroboration 913 by rearrangement of carbenes diacetoxylation 1007, 1009 aryl, and electrocyclic ring 1068 dialkoxylation 1008–1009 closure 1398 by reduction of thiiranes 1532 diamination 1021 arylation, flow reactions 831 by silyl-Wittig reaction 1191 dihalo, with DMF 720 mechanism 831 by the Bamford-Stevens alkenes, dihydroxylation 1005 metal catalyzed 811 reaction 1309 with metal acetates 1009 alkenes, as bases 349 by the Boord reaction 1320 catalysts for 1006 as nucleophiles 892 by the Corey-Winter reaction enantioselectivity 1008 asymmetric epoxidation, and 1316 in ionic liquids 394, 1006 manganese salen by the McMurry reaction 1597 regioselectivity 1008 complexes 1017 by the Ramberg-Backlund¨ alkenes, dimeric metathesis 1430 aziridination, enantioselective reaction 1316 dimerization 1445 1024 by the Shapiro reaction 1308 of carbenes 273 in ionic liquids 1024 by twofold extrusion with metals 942 organocatalysts 1024 1332–1333 dipolar addition with ozone Baker’s yeast reduction, by Wittig reaction 1194 1467 enantioselectivity 1521 alkenes, captodative 177 E-selectivity, Wittig reaction base induced elimination of carbene addition, rate constant 1199 alkyl halides 1311 1069 electrochemical elimination of bicyclic, strain 217 carbomagnesiation 946 dihalides 1318 bis(thiocyanato) 1000 carbonylation 984 electron donating groups, and bridgehead 217 metal catalyzed 984 Diels-Alder 1036 alkenes, by addition of catalytic hydrogenation 1513 electron withdrawing groups organometallics to alkynes chlorination, reagents 994 and Diels-Alder 1036 951 cis, from LDA and aziridino elimination of boranes 1314 by base induced elimination of hydrazones 1309 endocyclic 698 halo sulfones 1316 alkene, carbenoids 730 alkenes, epoxidation 493, 904, by bis(decarboxylation) of alkenes, conjugated see 906, 1010 dicarboxylic acids 1475 conjugated alkenes enantioselectivity 1016 by Chugaev reaction 1304 alkenes, conversion to alkynes reagents 1011 by cleavage of cyclic 1314 with chloramine-M 1014 thionocarbonates 1316 to allenes 1312 with sodium hypochlorite by Cope elimination 1307 to boronate esters 937 1017 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1928 SUBJECT INDEX

alkenes, erythro/threo addition from hydroxy-diazoketone hydrothiolation 923 893 1322 hydroxylation 912 exocyclic 698 from hydroxy-silanes 1191 hydroxysulfenylation 1018 fluorinated, [2+2]-cycloaddition alkenes, from lithio-silanes 1191 hydrozirconation 938 reactions 1066 from oxathiolanones 1332 insertion reactions 1168 fluorination 911 from phosphorus ylids 1194 intramolecular addition of formation of diols 1006 from radicals 263 alcohols 917 of lactones 1026 from selenoxides 1311 isomerization 699, 1445 of ozonides 1466 from sulfenes 1313 and riboflavin 909 of thiiranes 1018 from sulfonate esters 1305 asymmetric 909 more substituted 1288 from sulfones 1317 E/Z 908 alkenes, formylation 720 from sulfonyl halides 1314 metal catalysts 909 fragmentation of amines 1321 from thiophenes 1589 metal catalyzed 909 of halo ethers 1322 from vinylboranes, NaOH and positional isomers 908 free radical addition 896, 903 iodine 1388 alkenes, Jacobsen-Katsuki Friedel-Crafts acylation 719 from xanthate esters 1304 epoxidation 1017 Alkenes, from acyl halides 1315 alkenes, halo see halides, vinyl Julia-Kocienski reaction 1203 from aldehydes or ketones haloacylation 1005 lactam formation 1027 1194 haloacylation, and the Vilsmeier lactonization 1026 from alkanes 1446 reaction 1005 ultrasound 1026 from alkenes 1426 mechanism 1005 Lewis acid catalyzed addition of by sigmatropic migration halogenation 894, 910, 992 acyl halides 1005 1400 and bridged ions 992 addition of alkyl halides with alkenes 942 and Cinchona alkaloids 994 1003 by metathesis 1424 and fluorine 994 mechanism halohydrin from alkenyl boranes 1388 and radicals 992 formation 997 from alkynes 700 halonium ions 992 alkenes, metal catalyzed addition from allenes 1522 iodo- or bromosaccharin 997 of alkanes 940 from allylic silanes 545 mechanism 992 addition of alkenes 942 from amine oxides 1307 radical mechanism 995 addition of alkynes 942 from ammonium salts 1306 sterochemistry 994 addition of Grignard reagents from aziridines and nitrous acid the Prins reaction 1004 946 1318 UV 995 addition of silanes 940 from base elimination of ethers alkenes, halohydrins and addition to aldehydes 981 1301 Markovnikov’s rule 997 carboxylation 988 from betaines 1200 hindered, and carbenes 1070 decarbonylation of acyl halides from bisdithiocarbonates 1315 HOMO and LUMO 1044 1315 from bis-xanthates 1315 interactions 1045 elimination of halo ethers from boranes, mechanism 1314 homoallylic 427 1320 from carbenes 273 hydration 912 hydration 913 from carbenes 273 and Markovnikov’s rule 913 hydroamination 1020 from diazo compounds 1309 hydroamination 924 hydroformylation 989 from diazoalkanes 273 enantioselectivity 1020 with aryldiazonium salts 830 from diazoesters 1204 hydroboration 1521 alkenes, metal mediated from dicarboxylic acids 1475 alkenes, hydroboration, and elimination of dihalides and carbocations 1475 hydration 913 1318 from dihalides 1319 followed by aminating reagents addition to nitriles 1258 from diols 1316 928 alkenes, metals and alcohols from episulfides 1303 mechanism 736 1520 from episulfones 1317 preparation of boronate esters Michael addition, by Grignard from episulfoxides 1303 736 reagents, mechanism 963 from epoxides, electrolysis alkenes, hydrocarboxylation 984 of azides 931 1302 anti-Markovnikov 984 Michael-type addition, of enantioselectivity 1303 alkenes, hydrocyanation 991 hydrazoic acid 931 reagents 1302 hydrogen abstraction by migration, photochemical 699 from ethers 1301 radicals 852 η-complexes 1517 from halo amines 1321 hydrogen peroxide with formic nitriles and acylium ions 1026 from halo ethers 1321 acid 1006 nitro 1002 from halo sulfones 1317 hydrogenation with hydrazine nitroso-halogenation 1001 from halohydrins 1321 1521 nucleophilic addition 895 from homoallylic alcohols hydrometallation 937 orientation 1290 1328 hydromethylation 948 oxidation in the Wacker process from hydrazones 1308 hydrosilation 940 1499 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1929

to aldehydes or ketones, to alkanes, reagents 1519 with allenes 942, 1035 reagents for 1499 with diimide, mechanism 1521 with amides 927, 930 to allylic alcohols 1477 alkenes, reductive carboxylation with aryl disulfides, and metal oxidative cleavage 1467, 1470 982 salts 1018 with Lemieux-von Rudloff carboxylation, metal catalysts with arylboronic acids, metal reagent 1470 983 catalysis 803 Barbier-Wieland procedure alkenes, resolution 167 with boranes 735, 932–937, 1471 selectivity in catalytic 1314 mechanism 1471 hydrogenation 1515 steric effects 933 reagents 1472 Sharpless asymmetric with bromamines 1024 alkenes, oxidative decarboxylation epoxidation 1016 alkenes, with bromine 906, 1441 of carboxylic acids 1474 structural limitation 1017 and peroxides 1348 oxyamination 1019 Shi epoxidation 1014 substituent effects 900 oxymercuration 913 sigmatropic migration of alkenes, with carbene, IR 1068 ozonolysis 1466 hydrogen 1400 alkenes, with carbenes, to aldehydes or ketones 1466 simple, and the nucleophilic mechanism 1068 and rearrangement 1467 mechanism 899 rate constant 1069 Criegee mechanism 1467 stability 1288 sterochemistry 1069 mechanism 11467 stereochemistry 1290 steric hindrance 1070 Paterno-Buchi¨ reaction 1060 stereoselective addition of structural features 1070 photochemical boranes 933 alkenes, with carbocations 892 [2+2]-cycloaddition with structural effects, in the Heck with carboxylic acids 920 aldehydes 1060 reactions 814 Markovnikov’s rule 920 with ketones 1060 structure and asymmetric acids, metal catalyzed 920 photochemical isomerization epoxidation 1017 with catecholborane 969 328, 700 and dihydroxylation 1009 with CCl4, to from trihalides photochemistry 317 and ozonolysis 1466 484 geometry 328 symmetrical, and diimide with chiral dioxiranes 1014 alkenes, photoisomerization 328 reduction 1521 with chloramine-T 1019, 1023 protonolysis to from syn addition 904 with chloroformates 1005 carbocations 235 Takai reaction 1203 with carbon dioxide, π-complex 993 thermodynamic stability 698 carboxylation 987 π*-orbital 901 and metathesis 1425 with diazoacetates metal push–pull 177 twisted 220 catalyzed 1022 pyrolysis of amine oxides 1307 unsymmetrical, by McMurry with diimide 1521 of ammonium salts 1305 coupling 1597 with diisopinocampheylborane of homoallylic alcohols 1328 versus alkynes, hydrogenation 934 radical addition, and tetrahedral 1516 with diselenides 1018 mechanism 847 in ozonolysis 1467 with disiamylborane 934 anti-Markovnikov addition reactivity 901 with disulfides 1018 903 via Grob fragmentation 1322 with HBr and peroxides 910 generation of radicals 970 via Petasis reagent 1202 with HCl 349 radical halogenation 862 via Tebbe reagent 1202 with HX, Markovnikov radical-induced addition of alkenes, with 9-BBN 934 addition 910 polyhalo compounds 1004 with 9-BBN, regioselectivity phase transfer 911 reaction with acids 894 934 alkenes, with hydrazines 927 reaction, to give carbocations with acids, dimerization 942 with hydrazoic acid 931, 1374 894 HX 910 with hydrogen peroxide 1380 with acyl halides 720 with acylium ions 720 with hydroxylamines 927 with organometallics 946 with alcohols 916 with hypervalent iodine reactivity 899 base catalyzed 919 compounds 997 in alkene metathesis 1429 enantioselectivity 917 with hypohalous acids 996 in Diels-Alder reactions Markovnikov’s rule 916 with imido selenium 1036 mechanism 919 compounds 713 in the Heck reaction 814 photochemical 919 with imido sulfur compounds to metal catalyzed regioselectivity 916 713 hydroformylation 989 with alkenes 942 with isocyanates 1263 alkenes, reagents for oxidative metal catalyzed 981 with ketones 950 cleavage 1470 temperature and pressure intramolecular 950 to prepare halohydrins 996 939 with manganese acetate 1026 alkenes, reducing agents 1520 with alkyl azides 1022 with mCPBA 1010 alkenes, reduction by with alkyl nitrites 831 with mercuric acetate 913 hydroboration 1521 with alkynes 942, 1067 with metal hydrides 938 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1930 SUBJECT INDEX

alkenes, with hydrazines alkenylation, and metal carbene α-alkylation, to terminal triple (Continued) complexes 1203 bond 596 with mixed halogens 995 alkoxide bases, and ester enolate alkylation, acetoacetic acid with nitrosyl halides 1001 anions 1255 synthesis 577 with nitryl chloride 1002 and HSAB 362 alcohols, with ketones 584 with organocuprates 948 and Oppenauer oxidation 1450 aldehydes and ketones 580 with organolithium reagents with halo esters 1190 alkyne anions 597 947 alkoxides, and 1,3-elimination alkyne, metal catalyzed 597 intramolecular 948 1322 alkynes 596 with organomanganese and Grob fragmentation 1322 amides and sulfonamides 527 compounds 948 cleavage 751, 755 amines 589 with organometallic from ketones or aldehydes 249 Delepine´ reaction 515 compounds 948 gas phase cleavage 240 with alkyl halides 517 with organozinc compounds reaction with alkyl halides 490 and Montmorillonite clay 478 949 with alkyl sulfates 494 and radicals 477 with osmium tetroxide with aryl halides 781 and substitution 403 1005–1006 and microwaves 781 at carbon, enolate anions 479 with oxygen 914 with epoxides 497 at oxygen, enolate anions 479 oxygen, reactivity and structure with inorganic esters 494 alkylation, boranes 592 869 with trifluoroborates 783 metal catalyst 593 with permanganate 1006 alkoxy radicals 271, 851 alkylation, boronates 592 with peroxyacids 904, 1010 alkoxy-amination, of alkenes boronic acids 592 with phenols 916 1020 carbamate 588 with phosphines 928 alkoxyalkyl lithium reagents 243 carboxylic acids 586 with photosensitized oxygen alkoxyalkyl radicals 259 chiral enolate anion 579 868 alkoxyaluminum hydride, conjugated ketones 585 with polyhydrogen reduction of aldehydes and decarboxylative 755 fluoride–pyridine 910 ketones 1536 dianions 479, 578, 588 with potassium permanganate reducing agents 1536 dithianes 588, 1110 1005 alkoxyarylaminyl, radicals X-ray dithioacetals and dithioketals alkenes, with radicals 843, 846, 257 588 852, 912 alkoxycarbonylation 984 double 576 metal catalyzed 970 alkoxydithiocarbamates, and enolate anions 479 reversibility 898 radicals 841 and phase transfer 580 alkenes, with Selectfluor 911, alkoxyhalogenation 997 SET 578 1003 alkoxylation 490 SN2 578 with selenols 924 alkoxymercuration–demercuration enantioselective 581 with silyl halides, and DMSO 917 alkylation, ester enolates 584 999 alkoxymercuration, metal metal catalyzed 584 with silyl thiols 922 catalyzed 917 alkylation, exhaustive and amines with singlet oxygen 868 of alkynes 918 513 mechanism 870 of allenes 918 from oxazolines 592 with sulfonamides 930 of enol ethers 918 heterocyclic compounds 806 with sulfonyl chlorides 642 alkoxysilanes with aldehydes, hydrazones 585 with sulfonyl halides 999 metal catalysts 1105 inorganic esters 493 with sulfur reagents 999 alkoxysulfonium 1490 keto sulfones and keto with thiols 922, 1018 alkylation, bromoketones 592 sulfoxides 577 with thiophenol metal catalyzed 597 ketones, decarboxylative 585 anti-Markovnikov addition alkyl aryl coupling 560 lactones 582 922 alkyl chlorides see halides malonic ester synthesis 576 with tosylaziridines 1023 alkyl groups, and transannular alkylation, Morita-Baylis- with trialkylsilanes and acids rearrangement 1345 Hillman 1151 1520 stabilization of carbocations N, 2-pyrrolidinones 478 with trialkylsilyl halides 911 894 N, Oxazolidin-2-ones 529 with trimethylenemethane 1034 alkyl hydroperoxides, O and S, and flow reactions with triplet oxygen 868 decomposition 840 508 with water 912 alkyl hypochlorites, and radicals OversusC 576 Z-selectivity, Wittig reaction 841 O-, and enolate anions 576 1199 alkyl nitrites 710 O-alkylation 481 Zaitsev’s rule 698 alkyl sulfates see sulfates alkylation, of active methylene alkenyl boranes see boranes alkyl–alkyl coupling, Suzuki compounds 576 alkenyl-ketones, from Conjugated reactions 801 of aldehydes 579 alkynyl-ketones 962 α-alkylation, amines 590 of alkynes 951 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1931

of amides 1247 alkylidene oxetanes, with lithium addition of nitryl chloride metal catalysts 529 1135 1001 of amines 512, 590 akylidene-2-oxazolidinone, addition of Normant reagents with alkylborane reagents tautomerism 101 951 517 alkylidenebutenolides 1151 addition of organocuprates with diazo compounds 521 alkylidenecyclobutanes 730 951 of aromatic compounds 878 alkylidenecyclobutanone, from addition of organometallic of carboxylic esters 579 vinylidenecyclopropanes compounds 948 of conjugated compounds 961 1408 addition of sulfonic acids 921 of cyanide ion 600 alkylidenecyclohexanes, and addition of sulfonyl halides of dithianes 588 chirality 145 999 of enamine salts 587 alkylideneoxetanes 1061 addition reactions and of enolate anions 576, 579 alkyllithium see organolithium Markovnikov’s rule 911 of hydroperoxide anions 503 alkylnitrilium ions, reduction to alkoxymercuration 918 of imines 1122 amines 1557 alkylation 596, 930 of ketones 579 alkylsodium, with ethers 1301 alkynes, and alkene isomerization chiral amines 584 alkyltellurolates 510 916 Stork enamine reaction 587 alkyltrifluoroborates 735 α-alkylation 596 of lactams 529 alkyltrifluoroborates, coupling and anti-Markovnikov and microwaves 478 809 hydration 915 internal 529 alkyne acids, cyclization 1027 and Cadiot-Chodkeiwicz of nitriles 579 enantioselectivity 1026 reaction 876 of oxazines 591 alkyne allenes, via Stille coupling and Dotz¨ benzannulation 1079 of oximes 505 719 and flash photolysis 914 of phosphines 517 alkyne anions, ab initio study of and hydrogen bonding 110 of pyridine, with carboxylic 1,2-alkyl shifts 1349 and hyperconjugation 94 acids 880 acyl addition, and Cinchona and Michael reactions 957 of thiazoles and thiazolines alkaloids 1144 and oxymercuration 914 591 alkylation 597 and proton transfer 351 of thioamides 530 and Favorskii reaction 1144 and Stille coupling 718–719 pyrrole, in ionic liquids 515 Knoevenagel reaction 1187 and the Eglinton reaction 876 radical of aromatic compounds metal, with boranes 1388 and the Hay reaction 876 879 with aldehydes and ketones alkynes, anions 241 radical of aromatic compounds, 1143 with epoxides 573 mechanism 879 with aldehydes and ketones, alkynes, anti-Markovnikov reductive 1118 metal catalyst 1143–1144 hydroalkoxylation 918 S- 533 with aldehydes and ketones, as neighboring groups 427 sulfinic acid salts 511 solvent free 1144 Baker’s yeast reduction, sulfonate esters 589 with aldehydes or ketones, enantioselectivity 1521 sulfones 589 enantioselectivity 1144 bent 901 thioether carbanion 578 alkyne coupling, and chiral bis addition of organometallics vinyl sulfides 589 ligands 818 951 with active methylene cyclization 945 by elimination 1276 compounds 575 metal catalysts 945 by hydroboration, with diazo compounds 494 metal catalyzed 878 enantioselectivity 1388 with enolate anions 248 alkyne–aldehydes, with by oxidative coupling of with naphthoxide 481 organometallics 1143 dihalotoluenes 1508 with ynamines 578 alkyne–ketones, by by pyrolysis of acyl phosphorus alkylborane reagents, alkylation of Eschenmoser-Tanabe ring ylids 1308 amines 517 cleavage 1323 carbomagnesiation 946 alkylboronic acids see boronic conjugate addition of boranes, carbonylation 984 acids and boron trifluoride 969 catalytic hydrogenation 1516 alkylchloroaluminum amides, from epoxy hydrazones 1323 complex with mercuric salts formation of amidines alkyne–vinylcyclopropane 916 1126 metathesis 1430 conjugated, with silylcuprates alkylcopper–magnesium bromide alkynes, acyloxylation 1026 962 (Normant reagent) 951 addition of acids HX 911 alkynes, conversion to alkylidene carbenes 269, 728, addition of acyl compounds diphenylphosphino alkyne 1349 981 742 alkylidene cyclohexanes, and a addition of alkyl halides 1003 to enols 914 chiral axis 152 addition of HCN 991 to ketals 918 alkylidene lactams 975 addition of hypohalous acids to phosphonate esters 929 from ynamides 931 997 to vinyl halides 912 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1932 SUBJECT INDEX

alkynes, copper mediated addition of trialkylboranes 951 with ethers, microwave coupling 876 addition to alkenes 942 irradiation 939 coupling to give diynes 877 coupling reactions 597, 875 with Fischer carbene complexes coupling with amides 529 hydration 914 1079 coupling with propargyl Michael addition 966 with Grignard reagents 945 alcohols 876 with aryl halides 816 with heteroaromatic cross metathesis 1430 alkynes, metalated 597 compounds 949 cyclic poly-ynes 876 metathesis 1430 with HX 894, 911 cycloisomerization, mechanism nucleophilic addition 896 anti-Markovnikov 911 1078 oxidation to diketones 1501 alkynes, with hydrazines 928 cyclopropanation 1072 metal catalysts 1501 with hypervalent iodine 597 cyclopropyl, and radicals 256 reagents 1501 with hypohalous acids 997 dehydrohalogenation 1312 oxidative cleavage 1471 with imines 1164 diamination 1021 palladium catalyzed cross with indium reagents 949 dihydroxylation 1007 coupling 597 with iodo azide 1003 alkynes, from alkenes 1314 radical addition 970 with isonitriles 1169, 1264 from alkyl halides 596 reaction with dialkylaluminum with nitriles, cyclotrimerization from alkyne alkylation 596 reagents 938 1078 from alkynes, by metathesis reaction with organometallics with organolithium reagents 1430 938 947 from boranes 1314 reduction with Dibal 1522 with organometallic and metal alkyne anions with metals in ammonia compounds 948 1388 1522 with phosphines 928 from diarylthiiren-1,1-dioxides with sodium in ammonia with pinacolborane 936 1317 1522 with selenols 924 from selenoxides 1311 Rosenmund catalyst, and with silyl enol ethers 944 from vinyl halides 445 hydrogenation 1516 with silylboranes 941 alkynes, halogenation 995 silyl, as a protecting group 877 with sulfonamides 930 stereochemistry 995 terminal, base induced with sulfonic acids 923 alkynes, hydration 914 isomerization 700 with sulfonyl halides 999 and tautomerism 915 tetramerization 1076 with sulfur monochloride anti-Markovnikov catalysts metal catalysts 1076 1018 915 thiol 508 alkynes, with thiols 922–923 metal catalyzed 915 trimerization 1076 tolerable functional groups 923 alkynes, hydroacylation 980 diynes 1077 substituent effects 923 hydroalkylation 948 intramolecular 1077 alkynoic acids, decarboxylation hydroamination 927 metal catalysts 1076 754 metal catalyzed 927 alkynes, versus alkenes in alkynyl acids, decarboxylative hydroarylation 947 ozonolysis 1467 coupling, metal catalysts and flow reactions 950 hydrogenation 1516 888 hydroboration 740, 936 reactivity 901 alkynyl carboxylates, with reduction to alkenes 1522 alkynes, with acyl halides 598, dibromoalkenes 945 alkynes, hydrocarboxylation 980 alkynyl compounds, and 982–984 metal catalyzed 1156 nucleophilic substitution hydroformylation 990 alkynes, with alkenes 942, 1067 452 stereoselectivity 990 with alkynes 942 alkynyl ketones, conjugated, Alkynes, hydrogenation, metal with allenes 942, 927 hydroarylation 950 catalysts 1516 with amines, intramolecular alkynylaluminum 549 selectivity 1516 927 alkynylation, dienes 578 alkynes, hydrometallation 938 metal catalyzed 927 alkynyltrialkylborates 1389 hydrophosphinylation 931 with aromatic compounds 949 with methyl sulfate 1389 hydrosilation, Lewis acid with aromatic rings 1072 with triethyloxonium catalyzed 942 with aryl halides, metal tetrafluoroborate 1389 metal catalyzed 941 catalysts 950 potassium 568 Lindlar catalyst, and with arylboronic acids 951 alkynylzinc 549 hydrogenation 1516 with azides 1031, 1033 allenamides, isomerization, and mercuric catalyzed hydration, with aziridines 1033 Diels-Alder reaction 1054 mechanism 916 with B2(Pin)2 936 allene alkynes, via Stille coupling alkynes, metal catalyzed addition with boranes 1388 719 of arylboronic acids 951 with boronic acids 950 allene carboxylic acids 921 addition of Grignard reagents with carbenes 1072 allene esters 921 946 with cycloheptatrienes 1081 allene–alcohols, tautomerization addition of HCN 991 with dichloromethylsilane 941 444 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1933

allene–amines, intramolecular substituent effects 904 allylic compounds, ambident hydroamination 928 via allylic rearrangement 444 substrates 482 alleneols, with thiols 923 with alcohols, formation of and autoxidation 867 allenes 143 tetrahydrofurans 918 oxidation, and Bacillus allenes, [2+2]-cycloaddition intramolecular 919 megaterium 1480 1057–1058, 1066 with alkenes 942, 1035 oxidation, and ultrasound 1479 addition of chloroformates with alkynes 942 with oxygen 870 1005 with amines 988 π-allylic copper(III) complex 563 alkoxymercuration 918 with azides 1031 allylic halogenation, radical 862 amidation 930 with halo azide 1002 allylic oxidation, aldehydes, aryl, and alkyne migrations 700 with organomanganese reagents 1478–1480 and allylic cations 904 compounds 948 anaerobic 1480 and atropisomers 144 with radicals 904 of alkenes 1478 and Cahn-Ingold-Prelog system with thiols 924 of alkenes, with selenium 152 with vinyl sulfones 942 dioxide, mechanism 1482 and chirality 141, 144 allenic alcohols, carbonylation Sharpless method and selenium and cumulative double bonds 988 dioxide 1482 144 allenyl carbenoids 730 allylic radicals see radicals and electrophilic addition 904 allenylamines 516 allylic radicals 254–255 and formation of conjugated allenyltin reagents, and Stille allylic rearrangements see ketones 444 coupling 717 rearrangements and Meyer-Schuster allophanates, from carbamates allylic rearrangements 576, 694 rearrangement 444 1105 and propargyl systems 444 and mirror plane 144 allowed and forbidden reactions and SNi′ reactions 444 and Oxone 914 1049 formation of allenes 444 and the Pauson-Khand reaction allyl benzenes, conversion to halogenation 863 986 cyclopropylbenzenes mechanism 699 allenes, as neighboring groups 1432 SN2′ reactions 444 427 allyl carbanion, and resonance allylic substrates, and SN1 by allylic rearrangements 1319 43 reactions 452 mechanism 1320 allyl cation, and resonance 43 and SN2 rate of reaction 452 by metal catalyzed π-allyl complex, mechanism 700 and substitution reactions 452 rearrangement 1319 allyl halides see halides allylzinc reagents, with alkynes chiral 557, 700 π-allyl nickel-complex 563 949 cyclic 216 π-allyl palladium 1431 allyllithium reagents 115 epoxidation, with oxaziridinium complexes 44, 564 sulfur stabilized 248 salts 1014 allylic esters 564 allylsilanes, with aldehydes 1209 from alkenes 1312 reactions and mechanism 564 with aldehydes or ketones 1148 from alkynes 931 allyl radicals, and resonance 43 Sakurai reaction 1148 from carboxylic acids 886 electron diffraction 254 allyltin compounds, and from ketones 1217 allyl(trimethoxy)silane 966 enantioselectivity from organocuprates 556 allylation, decarboxylative, metal 1139–1142 from propargyl carbonates catalyzed 887 and ionic liquids 1138 1320 lactams 528 and organometallic compounds from propargyl ethers 1320 allylic carbocations, from dienes 1138 from propargyl tosylates 444 898 Keck allylation 1138 from propargylic alcohols 701 allylic acetates, and Pd catalyzed allyltrichlorosilane, with with boronic acids 1319 coupling 566 aldehydes or ketones 1149 from propargylic ethers 571 allylic benzyloxylation 1482 Aloe vera, and nitriles from halogenation 996 allylic bromination 864 aldehydes 1117 allenes, hybridization 144 allylic carbanions 239, 694 alternant hydrocarbons 68 hydroacylation 980 and LDA 1035 energy levels 69 hydrogenation 902, 1517 canonical forms 240 odd and even 69 hydrosilation 942 allylic carbocations 228, 694, odd and even, energy levels 69 in the Nazarov cyclization 959 1358 See also carbocations topological polarization 70 intermediates 700 and allenes 904 alternating axis of symmetry neighboring groups 427 canonical forms 441 136–137 Prins reaction 1214 resonance 441 alumina 477 rearrangement 909 allylic carbonates, and Pd and acetoacetic ester synthesis reduction 1522 catalyzed coupling 566 578 with sodium and ammonia allylic chlorination 863 and chlorination of lactams 765 1522 π-allylic complexes, with metals and conversion of aldehydes to Simmons-Smith reaction 1075 116 nitriles 1117 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1934 SUBJECT INDEX

alumina (Continued) with benzylic ammonium salts carbonylation of alkynes 988 and dehydration of alcohols 834 conjugated, for allylic amines 1299 with epoxides 523 765 and dehydration of oximes to with ketones 716 radicals coupling 874 nitriles 1325 with pyridine 823 amides, conversion to amines and elimination of alcohols to amide esters, by the Passerini 1370 alkenes 1301 reaction 1265 to diamines 1595 and elimination of ethers to amide-bridged calixarenes 120 to esters 1234, 1584 alkenes 1301 amides, acyloxy see amide esters to imides 1487 and Meerwein-Ponndorf-Verley amides, acidity 364 to indoles 1597 reduction 1539 acyl, from amino acids 756 to nitriles 1460 and reduction of nitro acylation 1248 amines, coupling with alkyl compounds 1560 with amines 1248 silanes 547 as a catalyst 506 addition to aldehydes 1122 coupling with alkynes 529 aluminum amalgam, sulfoxide alcoholysis 1234 dealkylation 1592 reduction 577 alkyl 519 decarboxylation to alkenes, aluminum complex, and alkylation 527, 1247 solvent free 1304 hydroxyalkylation 653 metal catalysts 5281 dehydration to isonitriles, aluminum compounds, and amides, and acidity scales 353 reagents for 1328 Meerwein-Ponndorf- and Caro’s acid 1111 to nitriles 1327 Verley reduction and catenanes 128 to nitriles, reagents for 1327 1538 and conformation 194 and Swern oxidation 1327 aluminum isopropoxides, and di(2-pyridyl)carbonate amides, dialkyl, aggregates 369 reduction of carbonyls 1243 and chelation 369 1538 and enantiomeric excess 174 and HMPA 369 aluminum-free, Meerwein- and Hofmann rearrangement as bases 369 Ponndorf-Verley reduction 1370 amides, diallyl, ene reaction 952 1539 and hydrogen bonding 112 electron delocalization 98 aluminum, dialkyl, with alkynes and isomers 177 enol content 98, 1527 938 and N-ylids 241 enolate anions 194 alumna, and microwaves, and proton transfer 351 exchange with carboxylic acids Suzuki-Miyaura coupling and pyramidal inversion 138 1236 800 and resonance 194 fluorination 764 Suzuki-Miyaura coupling 800 and rotaxanes 128 amides, from acyl halides and Amberlyst 15 498 and Selectfluor 1258 ammonia 1239 and acetal cleavage 488 and the Bouveault reaction from acyl halides with amines ambident nucleophiles see 1159 1239 nucleophiles and the Haller-Bauer reaction from alcohols 1257, 1494 ambident nucleophiles 480 759 from aldehydes and ammonia cyanide 600 and the Sonn-Muller¨ method to 872 ambident substrates see substrates prepare aldehydes 1558 flow reactions 1498 American Chemical Society: and the von Braun reaction from alkanes 873 ASAP papers 1608 1327 from alkenes and nitriles 1258 amidation of alkenes 930 and the zip reaction 1248 from amides 1247 amidation, and carbenes 873 and transamidation 1237 and aldehydes 872 aromatic compounds 637 and Wittig reaction 213 and amines 1237 of alkynes 930 microwaves, conversion to from amines 1488, 1494 of allenes 930 thioamides 1109 from anhydrides and ammonia oxidative 873 amides, aziridination 713 or amines 1240 amidazines, bases 349 amides, by amidation of alkenes from aryl iodides 669 amide bases 515, 1174 930 from arylboronic acids 669 amide bases, and enolate anion by carbonylation 669, 1249 from boronic esters 743 formation 721 by Chapman rearrangement from carboxylic acids and enolate condensations 1435 1241–1242 579–580 by hydration of alkynes 916 Burgess reagent 1242 and ketones 1253 by hydrolysis of isocyanates Lawesson’s reagent 1243 and Stevens rearrangement 1371 metal catalysts 1242 1381 of nitriles 1099 microwaves 1242 and the Haller-Bauer reaction by rearrangement of oximes reagents 1243 759 1375 amides, from esters 1245 chiral 370, 704 by solid-phase synthesis 1245 and ammonia or amines 1245 tetrasolvates 369 by the Willgerodt reaction 1604 and flow reactions 1246 with aldehydes or ketones 1172 amides, carbonylation 605 and high pressure 1246 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1935

and microwaves 1246 amides, Weinreb see Weinreb of organometallics 741 biocatalysts 1246 amides of phosphate 714 enzymes 1246 amides, with acyl halides 1249 amination, reductive 1118 ionic liquids 1246 with aldehydes 1184 See also reductive mechanism 1247 with alkenes 927, 930 amination amides, from esters, metal with amine salts 1247 metal catalysts 1119 catalyzed 1246 with amines 1238 reagents 1119 from imines 1435 with anhydrides 1250 amination, thermodynamic kinetic from imino esters 1435 with boronic esters 594 asymmetric 517 from isocyanates 669, 1168 with Grignard reagents 743, trifluoroborates 637 from ketenes and amines 1122 1158 amine alcohols, form amine from ketones 759, 1373, with hydride reagents 1552, halides 1367 1604–1605 1581 amine dehydrogenase, reductive from nitriles 1100 with hypohalites 1369 amination 1120 and alcohols 1257 with ketenes 1249 amine halides, with water 1367 from nitrilium ions 1377 with LDA 1184 amine oxides, and Boekelheide from organolithium reagents with organolithium reagents reaction 1383 743 1158 and Cope elimination 1307 from oxime esters 1377 with organometallics 1158 and Meisenheimer from oximes 1338, 1376 with phosphorus pentachloride rearrangement to oximes from phosphates 605 1435 1383 from pyrolysis of ammonium with sulfonamides 1249 and resonance 52 carboxylates 1241 with sulfonyl azides 713 and ylids 52 from sulfonamides 1249 with sulfurization reagents by oxidation of amines, from thioamides 1111 1238 reagents 1503 organometallics 743 amidines, from addition of pyrolysis to alkenes 1307 amides, Gatterman amide ammonia to nitriles 1126 reduction to amines, reagents synthesis 667 from ketenimines 1122 1586 amides, hydrolysis 1224 amidoalkylation, of aromatic with hydride reagents 1586 base-catalyzed reaction 1225 compounds 671 amine salts, resolution 169 DNA catalysis 1226 amidyl radicals 873, 975 with amides 1247 flow reactions 1224 aminals, carbenoid insertion 730 amine, diisopropylethyl see mechanism 1225 from hemi-aminals 1113 Hunig’s¨ base rate 377 amination of alkenes 924 amines, α-alkylation 590 reagents 1224 metal catalyzed 924–925 amines, acidity 364 tetrahedral intermediate 1225 with amines 924 amines, acylation 1240 to amines 1258 with ammonia 924 and Merrifield synthesis 1244 amides, keto-enol tautomerism 98 amination of, allylic CH 1487 and microwaves 1240–1241 magnesium or calcium 703 and microwaves 516 and Schotten-Baumann metal catalyzed synthesis 519 and pybox catalyst 516 procedure 1239 from amines to nitriles 1126 and Raney nickel 518 and ultrasound 1240 N-arylation 529, 789 and TosMIC 520 ionic liquids 1241 Goldberg reaction 789 amination, aromatic compounds polymer-bound 1241 N-halo, rearrangement 679 635 Weinreb amide 1241 nitrosation 761 and iodonium salts 635 amines, addition to alkenes 980, oxazolidine 1235 and microwaves 635 1021 radicals 842 ligand free 635 to isocyanates 1125 reaction with halogens 1371 metal catalyzed 635–636 to isothiocyanates 1125 reaction with hydroxide 377 amination, aryl chlorides 636 to nitriles 1126 reagents for reduction 1581 aryl hydrazines, flow reactions amines, alkyl halides and amides, reduction to alcohols 637 hexamethylenetetramine 1549 by Mitsunobu reaction 519 514 to aldehydes, reagents 1552 CH, of hydrocarbons 1487 amines, alkylation 512, 589–590 to amines 1549 electrochemical 873 Delepine´ reaction 515 catalytic hydrogenation 1582 heteroaromatic compounds 636 formation of diazo compounds Hantzsch esters 1581 amination, metal catalyzed 516, 823 reagents 1581 518, 636, 741–742 with alkylborane reagents 517 to aldehydes, Schwartz’s of alkanes 526, 713 with nitrous acid 823 reagent 1553 of alkenes, temperature effects amines, allenyl 516 amides, torsional barrier 194 924 amines, allylic, by SN2′ reaction twisted 213 of ketones, and microwaves with allylic carbonates via the Ritter reaction 1257 714 515 weak nucleophiles 527 asymmetric 714 CH amination 1487 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1936 SUBJECT INDEX

amines, allylic, by SN2′ reaction by Hofmann rearrangement amines, cyanation of 724 with allylic carbonates 1370 amines, cyclic, by reduction of (Continued) by hydrolysis of amides 1258 lactams 1582 formation of conjugated amides of cyanamides 1101 and carbonylation 765 765 of formamides 1258 cleavage with cyanogen from aldehydes 1151 of isocyanates 1370 bromide 544 from aziridines 526 by insertion reactions of amines from alkene–amines 515 amines, and carbamate formation 729 from haloamines 515, 1433 501 by metal reduction of ring expansion via Steven’s and differential hydration 371 hydroxylamines 1561 rearrangement 1381 and exhaustive alkylation 513 of nitro compounds, via the aza-Cope rearrangement and Katritzky mechanism 1559 1418 pyrylium-pyridinium by oxidation of CH 1486 von Braun reaction 544 method 512 by reduction of amides 1581 cycloalkyl, with nitrous acid and leaving groups 466 Hantzsch esters 1581 1356 and Menshutkin reaction 513 reagents 1552, 1564, 1581 dealkylation 1591 and nitrous acid 466 of azo compounds 1565 reagents 1592 and proton transfer 351 of C=N compounds 1553 deamination 1580 and pyramidal inversion 138 of carbamates 1583 reagents 1585 and racemization 140 of diazonium salts 1565 dehydrogenation 1461 and resonance 365 of hydrazones 1553 reagents for 1460 and the Bruylants reaction 568 of imines, reagents 1553 diazotization 467, 1339 and the Hinsberg test 1269 of isocyanates 1565 and rearrangements 1339 and the Staudinger reaction of isothiocyanates 1565 dicarbonyl, as nucleophiles 1565 of nitriles, 479 and the von Braun reaction polymethylhydrosiloxane ditosyl, with halide ions 543 544 1582 energy barrier to pyramidal and transamidation 1237 reagents 1556 inversion 138 the interrupted Nazarov 958 transfer hydrogenation 1582 fluorination 764 amines, aromatic see anilines of nitro compounds, reagents amines, formation by metal amines, aromatic, with epoxides 1558 catalysis 514 522 with metals in acid 1559 of alcohols 505 amines, aryl 516 of nitroso compounds 1565 of onium salts 358 by the Bucherer reaction 790 of oximes, reagents 1562 of Schiff bases 1112 from phenols and naphthols of Schiff bases 1553 amines, formylation 1247 790 of semicarbazones 1563 amines, from acyl halides 1372 from phenols, SRN1 mechanism of iminium salts 1554 from addition of amines or 790 amines, by reductive alkylation ammonia to alkenes 924 rearrangement with 1118 from alcohols 518 organolithium reagents amines, by Stevens rearrangement from alkenes 928 1384 1381 from alkylnitrilium ions 1557 with nitrous acid 824 amines, carbamoyl 1238 from amides 1370, 1549 mechanism 825 amines, carbonylation 764 amines, from amides 1552 amines, arylation 635 and electrolysis 765 and Grignard reagents 1159 Buchwald-Hartwig Cross with alcohols 765 and organometallics 1159 Coupling Reaction 786 amines, chiral 140 catalytic hydrogenation 1582 chiral 787 from formamidines 590 amines, from amine oxides 1586 flow reactions 786 ketone alkylation 584 from amino ethers 570 in ionic liquids 786 with carboxylic acids 584 from ammonium salts 1381 intramolecular 786 amines, chloro, from amines 763 from azetidines 574 metal catalyzed 786–788 amines, conjugate addition 976 from azides 741, 1564 amines, as ligands 44 and transition metals 976 from aziridines 574 basicity 349 enantioselectivity 979 metal catalyzed 1318 basicity in solution 371 amines, conjugate base formation from azo compounds 1592 bridgehead, and chirality 139 1171 from azoxy compounds 1592 amines, by Mitsunobu reaction amines, conversion to amides from boranes 928 517 1494 from carbocations 526 by base induced rearrangement to enamines 1446 from Grignard reagents 568, of ammonium salts 1381 metal catalysts 1446 570 by catalytic hydrogenation of to imines 1461 from hydrazo compounds 1592 nitriles 1557 metal catalyzed 1461 from hydrolysis of isocyanates by CH oxidation of to isonitriles 527 1372 hydrocarbons 1486 to triazenes 762 from hydroxylamines 1561 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1937

from imines 1162, 1553, 1555 to hydroxylamine, with Caro’s intramolecular 927 enantioselectivity 1166, acid 1502 metal catalyzed 927 1555 enzymes 1503 with allenes 988 metal catalyzed 1165 reagents for 1502 with amides 1238 with alkynes 1164 to imines 1491 with anhydrides 1240 with boronates 1165 to ketones or aldehydes with anhydrides, tetrahedral with boronic acids 1165 1491–1492 mechanism 1240 with nitro compounds 1166 to lactams 1488 with aryl fluorides, and with silanes 1165 to nitriles 1460 ultrasound 786 amines, from iminium salts 1165 to nitro compounds, reagents with aryl triflates 785 from isocyanates 1372–1373 1503 with aryl triflates, and from isonitriles 1557 to nitrones 1462 microwaves 786 from nitriles 1169 reagents for 1492 with aziridines 525 and photochemistry 1557 amines, palladium catalyzed, from with benzyl chloroformate and transfer hydrogenation allylic carbonates 515 1240 1557 amines, photochemistry 317 with boron trifluoride 1247 amines, from nitro compounds amines, propargylic, by SN2′ with bromoacetophenone 454 1558–1559 reaction with allylic with calcium, reduction of flow reaction 1560 carbonates 515 aromatic compounds 1526 hydrosilation 1561 amines, reaction with aldehydes or with carbon dioxide 765 photochemistry 1561 ketones 1111 with carbon disulfide reagents 1560 with alkyl halides 517 1126–1127 reductive alkylation 1561 with KOH 505 with carbon monoxide 764 transfer hydrogenation 1560 with Mannich bases 520 with carbonates 1241 amines, from nitroso compounds with nitrous acid 235 with chloroformates 1240 1561 amines, reactivity differences with with cyanamide 522 from organoboranes 741 halides 514 with cyanogen bromide 544 from organometallics 741–742 amines, reduction of imides 1583 with cyclic anhydrides 1241 from oximes, reagents 1562 of oximes, reagents 1562 with cyclopropane 526 from phosphonates 590 to amines, reagents 1553 with diazo compounds 521 from trifluoroborates 1169 to hydrocarbons, reagents 1585 with dimethyl(methylthio) Gabriel synthesis 529 amines, reductive amination with sulfonium salts 1025 gas phase basicity 371 aldehydes or ketones 1118 with epoxides 522 Grignard reagents complex 747 amines, replacement with alkyl microwaves 522 halo, and Grob fragmentation 830 with esters 1245 1322 amines, secondary, with ketones with esters, and high pressure fragmentation 1321 1113 1246 from amines 763 amines, substitution of aryl with formaldehyde and phenols with acid 1434 halides 769 671 amines, Hofmann-Loffler¨ reaction of aryl halides, base catalysis with formic acid and iodine 1433 769 1239 hydrogenolysis 1584 amines, tertiary, from primary with hypohalites 763 hydrolysis of isocyanates 1373 amines 517 with ketenes 1122, 1364 Ing-Manske procedure 530 amines, transamination 520 amines, with lactams, high insertion reactions 729 amines, via aza-Baylis-Hillman pressure 1247 kinetic resolution 171 reaction 1166 with lactones 1247 metal catalyzed carbonylation via aza-Baylis-Hillman reaction, with Lewis acids 526 764 enantioselectivity 1166 with lithium, reduction of addition to nitriles 1126 via benzyne intermediates 786 aromatic compounds 1526 methylation, and boronic acids amines, with acyl halides 1239, with microwaves 513 516 1313 with Na or Li 1520 Michael addition 976 with aldehyde–carboxylic acid with nitrites 1492 migration 1367 1184 with nitro-ketones 759 N-nitroso derivative 590 with aldehydes and alkyl with nitronium salts 761 nitrosation, mechanism 761 halides 1120 with nitrous acid 761, 1357 of ketones 1488 with aldehydes or ketones with organolithium reagents overmethylation 514 1111, 1118 1383 amines, oxidation 1462 with aldehydes or ketones, with oxetanes 524 of amides, solvent free 1488 metal catalyzed 1112 with phosgene 1239 of manganese dioxide 1462 with aldehydes, NBS-AIBN with sulfonyl halides 1269, to amides 1488 872 1313 to amine oxides, reagents with alkyl halides 513 to give sulfenes 1314 1503–1504 with alkynes 927 formation of sulfenes 1267 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1938 SUBJECT INDEX

amines, with lactams, high aminocarbenes 269 with metals, and decyanation pressure (Continued) aminocarbonylation, and 760 with tert-butoxy anhydride microwaves 669 with sulfonyl halides 1269 1240 aminochlorination 1000 ammonium carboxylates, from with thiiranes 523 aminocycloalkenes 1217 carboxylic acids 1242 with thiophosgene 1240 aminohalogenation 1001 ammonium formate see formate with tricarbonates 764 aminohydroxylation, and ammonium hydroxide, with with tropylium (DHQ)2PHAL 1020 epoxide and microwaves tetrafluoroborate 724 and hydrochlorites 1020 522 aminium radical cations 860 enantioselectivity 1020 ammonium salts, alkyl amino acids, and chirality 148 of alkenes 1019 rearrangement 680 conversion to acyl amides 756 phase transfer 1019 allylic, rearrangement 1421 conversion to lactams 1243 Sharpless asymmetric and amide hydrolysis 1224 decarboxylation 754 1019–1020 and Cope elimination 1383 diazotization 543 aminoketones, from and formation of aldehydes and flow chemistry 337 Eschenmoser’s salt 913 from azido acids 713 1124 and Hofmann elimination 1305 amino acids-boric acid, and aminolysis, of thiolactones and Hofmann-Martius reaction resolution 167 1247–1248 680 amino-Cope rearrangement 1409 aminomalononitriles 1213 and indirect hydration 914 amino-hydroboration 928 aminomercuration 928 and phase transfer catalysis 475 anti-Markovnikov addition 928 Markovnikov addition 928 and Stephens rearrangement amino alcohols see of alkenes 1020 835 hydroxyamines aminomethylation, and Stevens, rearrangement amino alcohols, and cyclodextrin anti-Markovnikov 925 1381 523 aminomethyl aromatic and syn elimination 1278 and microwaves 522 compounds 834 and the Knoevenagel reaction by electroreduction 1596 aminomethylation, of aryl halides 1187 conversion to aziridines 519 671 base induced rearrangement enantioselective formation 522 pyridine derivatives 671 1381 epoxides with amide bases 523 aminophenols, from oximes 836 benzylic, and Sommelet-Hauser from aldehydes 1595 from the Bamberger rearrangement 835 from amines 524 rearrangement 836 benzylic, rearrangement 834 from azide-alcohols 523 aminophosphonates, from chiral 1212 from epoxides 522–523 phosphates 714 chiral, and formation of from ketones 1596 aminopyrenyl radical, and X-ray aziridines 1023 from oxetanes 524 257 chiral, with HCN 1212 lithium perchlorate in ethers aminopyridine, from pyridine cleavage 501 523 823 from amines and alkyl halides solvent free preparation 522 aminosulfenylation, nucleophiles 514 with nitrous acid 1357 1025 halo, heating 1434 amino ethers, alkoxy-amination of of alkenes 1024 heating, formation of alkyl alkenes 1020 aminoxyl radicals 258 halides 544 from alcohols 498 aminyl radicals 975 pyrolysis 1306 from aziridines 498 ammonia, addition to cyanamide pyrolysis to alkenes 1305 amino ketones, by the Mannich 1126 quaternary, and out–in isomers reaction 1123 addition to nitriles 1126 181 by the Neber rearrangement and pyramidal inversion 138 cleavage 509 1369 and sodium, reduction of molten 476 amino leaving groups, in Mannich alkynes 1522 thermal stability 476 bases 466 basicity in solution 371 rearrangement 835 amino nitriles 1212 bond angles 7 reduction to hydrocarbons 1585 Bruylants reaction 568 liquid, and carbon acids 347 with base 1307 with Grignard reagents 568 metals, reduction of alkynes ammonium thiocyanate, α-amino radicals, persistent 1125 1522 conversion to thiocyanates amino thioethers, from aziridines supercritical 393 533 498 with acyl halides 1239 amphiprotic properties 701 amino thiols, from epoxides 523 with aldehydes or ketones 1111 anchimeric assistance 433 aminoalanes, with carboxylic with alkyl halides 513 and cyclopropyl 429 acids 601 with anhydrides 1240 and SN2 reactions 422 aminoalkylation, and the Mannich with carboxylic acids 1241 solvolysis 427 reaction 671 with epoxides 522 angle strain, and cyclobutanes 209 of aromatic compounds 671 with esters 1245 angles, bond see bond angles JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1939

angles, bond, and anhydrides, with alcohols 1227 oxidation to azo compounds bicyclo[1.1.0]butane 209 with alcohols, catalysts 1228 1461 and cyclopropane 208 with alcohols, metal catalysts to nitroso compounds 1502 and cyclopropene 215 1228 with Caro’s acid, mechanism and prismane 212 with aldehydes 1190 1502 and s character 28 with amides 1250 pKa 366 and steric strain 206 with amines 1240 replacement of amino with and twisted alkenes 220 tetrahedral mechanism 1240 alkyl 830 bromoalkanes 27 with ammonia or amines 1240 ring closure with aldehydes or methane 9 with boronic acids 1156 ketones 1113 table 28 with ethers 502 with aryl nitroso compounds angles, dihedral, and with hydrogen peroxide 503 829 conformation 193 with inorganic acids 1236 with hyponitrites and allyl angles, torsion, and conformations with ketones 1253 halides 830 189 with silyl enol ethers 1253 with thiols, flow reactions 784 and molecular mechanics 204 with sulfonamides 1241 anion relay chemistry 1110 and specific rotation 136 anilides, from benzamides 669 1,3-anionic cycloadditions 1034 dihaloethanes 190 from heteroaryl carboxamides anionic oxy-Cope rearrangement angular momentum, and 669 1409 intersystem crossing 323 anilines, acyl, halogenation 679 anionic Snieckus-Fries angular polyacenes 61 Orton rearrangement 679 rearrangement 677 anhydride, acetic, with DMSO anilines, ammonium salts, and anions, cyclopropenyl 237 1603 rearrangement 680 anions, cyclopropyl 243 anhydride, benzeneseleninic 716 Hofmann-Martius reaction anions, enolates see enolate anhydrides, alcoholysis 1227 680 anions enantioselectivity 1228 metal mediated rearrangement anions, methyl 243 microwave irradiation 1228 680 N-nitro, rearrangement, isotopic anhydrides, and the Perkin photolysis 680 labeling 677 reaction 1190 anilines, and alkyl halides 514 retention of configuration 243 anhydrides, cyclic, from and Hofmann-Martius reaction anisotropy, and alkenes 56 dicarboxylic acids 1228 680 and aromatic compounds 55 from dicarboxylic acids 1236 and hydroxylation reactions and cyclophanes 55 with amines 1241 674 magnetic 55 anhydrides, dehydration of and nitrous acids 634 and NMR 19 carboxylic acids 1235 and Reilly-Hickenbottom annellation 61 anhydrides, from acyl halides with rearrangement 680 and cyclopentadiene 64 carboxylic acid salts 1235 and resonance 48 and strain 51 metal catalysts 1235 and the Mills reaction 829 Annual Reports in Organic phase transfer 1235 anilines, azo compounds 679 Synthesis 1624–1625 ultrasound 1235 Boyland-Sims oxidation 674 Annual Reports on the Progress of anhydrides, from acyl peroxides canonical forms 48 Chemistry 1623 871 conversion to aryl fluorides, annual reviews 1623 from aldehydes 871 flow reactions 647 annulation reactions 1180 from carboxylic acids 1235 deamination, by reduction of [6+2]-annulation, and Brook and enol esters 1236 diazonium salts 1587 rearrangement 1438 from phosgene and carboxylate diazotization, mechanism 823 annulene-ones 86 salts 1236 electron density potential map annulenes, aza see azaannulene from twisted amides 1235 48 annulenes, dehydro see hydrolysis 1218 Fischer-Hepp rearrangement dehydroannulenes mixed organic–inorganic, from 678 annulenes 50, 82 anhydrides 1236 anilines, from amines 785 annulenes, adding electrons 71 phosphorus 1236 aryl triflates 785 annulenes, and alkyne coupling sulfonyl 1236 anilines, from aromatic nitro 876 with amines 1241 compounds, reagents 1560 and antiaromaticity 74, 85–86 anhydrides, reaction with from aryl halides 785 and aromaticity 71, 76, 79, 81, aldehydes 1104 from diazo compounds 1555 83–84 with sulfoxides 1603 from N-nitroamines 677 and chiral axis 152 anhydrides, reduction to from oximes 836 and Hartree-Fock calculations aldehydes 1551 halogenation 644 78 to aldehydes, reagents 1551 N-nitro, rearrangement, and and HPLC 89 to lactones, reagents 1580 radicals 677 and Huckel’s¨ rule 77 anhydrides, tert-butoxy, with N-nitroso, rearrangement 678 and Mobius¨ aromaticity 88 amines 1240 nitration 632 and NMR 78, 81, 84, 86 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1940 SUBJECT INDEX

annulenes, and alkyne coupling addition, hydration of alkynes ethanolysis, SN2, alkyl halides (Continued) 915 378 and planarity 79 addition, hydroboration of micellar medium, alkene and the Eglinton reaction 876 alkenes 913 metathesis 1428 and X-ray crystallography 83, addition, radical addition to solution, SN2, free energy 87 alkenes 903 profile 408 antiaromaticity 89 addition, radicals to alkenes Arbuzov reaction 1198 aromatic substitution 80, 83 970 arene azides 532 aromaticity 82 addition, thiols to alkenes 922 arene lithiation 806 atropic 87 catalysts, hydration of alkynes arenediazonium salts, with bond alternation 87 915 arylselenenol, preparation bond angles 78 hydration of alkenes 913 of diarylselenides 785 bond distance 83, 87 hydroalkoxylation, of alkynes arenes see aromatic compounds bond length 81 918 arenes, by Friedel-Crafts bridged 83, 87 orientation, hydroboration 740, alkylation 648 conformational mobility 85, 87 1385 coupling with diaryliodonium conformations 78 selectivity, metal catalyzed salts 803 annulenes, definition of 71 hydrosilation 940 from aromatic compounds 878 dehydro 76 anti-nomenclature 161 from aryl halides 805 diatropic 80–84 antiaromatic compounds, and from aryl organometallics 805 heat of combustion 87 bond distance 57 arenium ion mechanism 607–608 isomers 77 antiaromaticity 73 biaryls 810 N and O analogs 79 ab initio calculations 71 rate 610 NMR 87 and annulenes 74, 86 arenium ions 228, 232–233, 608 paratropic 86–87 and cyclizes 86 ab initio study 611 planarity of 87 and cycloheptatriene anions 77 activating groups 614 strain energy 79 and indacene 86 and aromaticity 609 triplet 72 and methanoannulenes 86 and carbocations 608 twist conformations 78 and NMR 74, 87 and deuterium ions 610 cations 90 and paratropic compounds 87 and encounter complexes 613 annulenes 77, 82 and ring current 56 and Lewis acids 612 anomeric effect 200–201 and stability 73 and resonance 608 and 2nd row heteroatoms 202 cyclobutadienes 73 and steric hindrance and and hyperconjugation 201 dipleiadiene 87 deprotonation 610 and parallel dipoles 201 for cyclobutadiene 39 and superacids 611 and solvation 201 MO calculations 71 and the E1 mechanism 607 extended 1088 oxiranes 1015 and σ-complexes 608 radicals 259 antibody catalyzed, [3+2] aromatic halogenation 643 antarafacial, bond formation, cycloaddition 1035 charge densities 619 Diels-Alder reaction 1050 Diels-Alder reaction 1037 deactivating groups 614 HOMO-LUMO, oxy-Cope rearrangement 1410 deuterium exchange 612 [4+2]-cycloaddition 1051 antibonding orbitals 5 dienone-phenol rearrangement migration, in sigmatropic allylic carbocation 42 1360 rearrangement 1401 anticlinal conformation 190 ipso position 620 rearrangements, configuration antihomoaromatic compounds 91 isolation 610 of migrating groups 1405 antimony, and optical activity 140 isotope effects 609–610 anthracene compounds, as host antimony pentafluoride, and cation mechanism, evidence for 609 125 stability 225 meta substitution, −I 615 and resonance 49 antimony pentafluoride and naphthalene 623 resonance energy 60 FSO3H 347 ortho substitution, −I 615 with bromine 60 antioxidants, and autoxidation para substitution, −I 615 anti-addition 892–893 867 partition factor 610 anti-aldol reaction 1184 antiperiplanar, conformations 190 partitioning effects 609 anti-Bredt alkenes 1196 antipodes 134 reaction with nucleophiles 633 anti-elimination, and dihedral apparatus, hydrogenation 1514 resonance interaction of angle 1277 apparent 1,3-hydride shift 1344 substituents 615 anti-Markovnikov, addition Appel reaction 538 stability 611 alkenes, aprotic solvents 469 table 612 hydrocarboxylation 984 and hydrogen bonding 110 stable solutions 611 with thiophenol 922 aqueous, aldol condensation 1177 arenonium ions 233 addition, and boranes 933 detergent solutions 391 argon matrix 216 addition, HBr, peroxides, and Diels-Alder reaction, catalysts and carbenes 268 alkenes 910 1037 argon, as a guest 124 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1941

argon matrix, trapping carbenes, by Friedel-Crafts alkylation oxidative cleavage, reagents spectra 1365 648 1472 Arndt-Eistert synthesis 1363 by reduction of diazonium salts, phenylenes 51 and diazomethane 712 reagents 1587 phosphorylation 637 and Wolff rearrangement 1364 by reduction of phenols 1572 photochemical coupling with Curtius rearrangement 1364 by reversal of Friedel-Crafts aryl halides 879 enantioselectivity 1364 alkylation 681 π interactions 113 ketenes 1364 aromatic compounds, canonical radical alkylation or arylation lactams 1364 forms 60 879 Wolff rearrangement 1364 catalytic hydrogenation 1523 reaction with alkyl halides 648 aromatic carbocations 230 coupling with aryl halides 880 reactivity 614, 626 aromatic carboxylic acids see coupling with diazonium salts with radicals 854 carboxylic acids 638 catalytic hydrogenation 1524 aromatic chameleons 68 cyanation 672 aromatic compounds, reduction aromatic character 54 cyclotrimerization of alkynes with lithium and ammonia aromatic compounds, acenes 61 1076 1524 activation groups 614 decarbonylation 683 with lithium and ammonia acyloxylation 871 deuteration 630 1524 alkyl substituents see benzylic diazotization, and phase with metals and ammonia 1524 alkylation 879 transfer 639 with potassium and ammonia and CIDNP 879 dihydroxylation 1010 1524 mechanism 879 distorted 50 with sodium and ammonia amidation 637 electrolysis, formation of 1524 aminoalkylation 671 phenols 674 aromatic compounds, replacement aminomethyl 834 enantioselectivity, catalytic of nitro with alkyl 834 aromatic compounds, and hydrogenation 1524 ring expansions 1024 anisotropy 56 formation of biaryls 657 six-membered rings 58 and annellation 61 formation of nitriles 672 strained 51 and aromaticity 54, 58 formylation 663, 665 and rotation barrier 219 and Benkeser reduction 1526 aromatic compounds, from sulfonation 639–640 and benzylic hydrogens, with aromatic compounds 879 metal catalyzed 641 radicals 852 from aryl organometallics 685 tormented 51 and Birch reduction 1524 from ene-diynes 1395 tritiation 630 and deactivating groups 614 from sulfonic acids 1589 twisted 51 and electron donor–acceptor fused ring 51 UV and IR, and strain 218 complexes 114 fused, and bond distance 60 aromatic compounds, with acyl and field effects 22 and carbanions 240 peroxides 878 and geared molecules 219 halogenation 642 with acyl peroxides 879 and hydrogen exchange 630 hydroxylation 674, 865 with alkynes 949 and MO calculations 35 with Udenfriend’s reagent with aryl diazonium salts 831 and NaCl 124 865 with calcium and amines 1526 and phenonium ions 431 and Lewis acids 674 with carbenes 271 and Pseudomonas putida 1010 Elbs reaction 674 with chlorosulfuric acid 641 and radicals, mechanism 845 potassium persulfate 674 with Fenton’s reagent 865 and resonance 35, 49 aromatic compounds, metal with fulminates 672 and restricted rotation 220 catalyzed hydrogen with hydrogen peroxide 865 and strain 218 exchange 630 with hypervalent iodine 646 and sulfuric acid 639 metalation 675 with isocyanates 669 and the Baker-Nathan effect methyl see methyl aromatic with lithium and amines 1526 93 Mills-Nixon effect 51 with metals and amines 1526 and the Dakin reaction 1473 nitration 630 with nitrate esters 631 and π–π interactions 113 and arylboronic acids 633 with nitriles 672 aromatic compounds, aromatic radical pair formation 633 with nitrous acid 638 character 54 nitro, from N-nitroanilines with peroxyacids 674 aromatization of six-membered 677 with phosphorus compounds rings 1442 nitroso 678 637 arylation 657 organometallics with aryl aromatic compounds, Wurtz-Fittig bond alternation 51 halides 559 reaction 549 aromatic compounds, by Bergman ortho-meta-para substitution aromatic deprotometalation 685 cyclization 1395 614 aromatic diazonium compound by decarboxylation 683 oxidation of side chains, alkyl 638 by electrocyclic ring closure group reactivity 1473 aromatic diazonium salts see 1398 oxidation to quinones 1489 diazonium salts JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1942 SUBJECT INDEX

aromatic fluorination 647 and cycloheptatriene anion 77 Huckel¨ 88 aromatic formylation, metal and cyclooctatetraene 70, 77 index 63–64 catalyst 664 and cyclopentadienide ion 62 local 64 β-aromatic groups, and and cyclopentadienyl cation 75 mesoionic compounds 89 neighboring groups 433 and cyclophanes 50 Mobius¨ 88 aromatic halogenation, and ionic and cyclopropenyl anion 75 nonaromatic systems 71 liquids 644 and diamagnetic ring current 55 of benzene 39 and NBS 645 and diamagnetic ring current 57 parameters 71 and ultrasound 644 and diatropic 54 pentalene 67 metal catalyzed 644 and distortion 50 phenacenes 85 reactivity of halogens 642 and fulvalenes 68 relative, for benzene 39 Sandmeyer reaction 645 and furan 62 spherical 91 aromatic index see aromaticity and heptalene 67 spherical homoaromaticity 91 index and heteroaromatic compounds squaric acid dianion 90 aromatic iodination 645 58, 63 superaromatic 84 aromatic rings, as neighboring and Huckel’s¨ rule 71, 76 sydnones 89 groups 430, 432 and Hund’s rule 71 trihomoaromatic 91 bond distance 41 and hybridization 51 tropone 65 cyclopropanation 1073 and hyperconjugation 94 Y 41 strain and deformation 624 and isotope labeling 65 aromatics, contorted 56 with alkynes 1073 and methanoannulenes 80 polycyclic, FVP 1399 aromatic sextet 54, 58 and molecular refraction 64 aromatization, and Hantzsch and benzene 35 aromaticity, and naphthalene 61 dihydropyridines 1445 and heterocycles 61 and nitrogen heterocycles 58 and metal catalysts 1443 aromatic side, chains, oxidation, and NMR 55, 81 and selenium 1443 mechanism 1473 and nonplanarity 80 and Sonogashira coupling oxidation, reagents 1473 and paramagnetic ring current 1444 aromatic stabilization energies, 57 and sulfur 1443 arynes 774 and partial bond fixation 59 by Bergman cyclization 1395 aromatic sulfonation, mechanism and phenalene 60 by chloranil 1443 640 and phenanthrene 60 by DDQ 1443 SEAr 640 and planarity 83 by dehydrogenation 1444 aromatic π-cloud 34 and polyacenes 61 by quinones, mechanism aromaticity 54 and pyrenes 83 1443 aromaticity index, and and pyridine 59 isotope effects 1443 delocalization energy 57 and pyrrole 62 of cyclohexenes 1442 and fulvalenes 68 and resonance energy 63 of enamines 1445 fulvalenes 68 and ring current 54 of six-membered rings 1442 heterocycles 63 and the conjugated-circuit reagents 1443–1445 aromaticity, absolute 39 model 58 to form heterocycles 1444 aromaticity, and absolute hardness and the hardness model 58 with quinones 1443 64 and the Herndon model 57 Arrhenius activation energy 303 and annellation 61 and the Hess-Schaad model 57 arsenic, and optical activity 140 and annulenes 50, 71, 76–78, and the pyrylium ion 58 arsine ylids 1197 81–84 and the SCF method 59 arsines, and ylid formation 1197 and arenium ions 609 and the tropylium ion 67 arsonium ylids, with tosylimines and aromatic compounds 54, and thiophene 62 1208 58 and triphenylene 61 Arthrobacter sp. AD2, Halohydrin and arynes 774 aromaticity, annulenes 79 dehalogenase 523 and azaannulenes 80 aromatic character 54 aryl alkyl coupling 560 and Bader’s electron aromatic sextet 58 sulfides 508 delocalization index 64 azulene 67 alkyl tellurides 510 and Baird’s theory 68 bishomoaromatic 91 aryl cations 829, 832 and benzenoid hydrocarbons 57 C- 96 aryl formylation 663–666 and benzoannulenes 82 cyclobutadiene metal complex aryl groups, and radical and benzynes 774 75 rearrangement 1346 and bond alternation 65 cyclopropenyl cations 72 migration and radical and bond order 64 fullerenes 91 delocalization 1347 and calicene 68 fused ring aromatic compounds transition state of and chemical shift 55 64 rearrangement 1347 and circuit resonance energy 57 heptalene 67 aryl halides, and hyperconjugation and cyclobutadiene 70 heterocycles 63 46 and cyclodecapentaene 71 homoaromatic compounds 90 and resonance 46 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1943

aryl nitro compounds, and the sulfonamides 590 propargylation 596 Sandmeyer reaction 829 sulfones 590 reduction, of prochiral ketones aryldiazonium salts 829 with active methylene 1542 aryl organometallic compounds compounds 575 transfer hydrogenation 1554 685 arylazo group, migration 679 synthesis 161–166, 358 aryl radicals 826–827, 832, 854 arylboronic acids see boronic asymmetric atom see chiral, See also radicals acids, aryl stereogenic and diazonium salts 826 arylboronic esters see boronic asymmetric, epoxidation see regioselectivity, rate, table 855 esters, aryl epoxidation aryl sulfones, from sulfinic acid aryldiazonium salts 532 asymmetric, induction see salts and aryl iodides 784 aryldiazonium salts, by flow enantioselectivity aryl triazenes 639 reactions 647 asymmetric, reactions see arylamines 516 aryllithium see organolithium, enantioselectivity arylamines, and thermodynamic aryl asymmetric, synthesis see kinetic asymmetric aryllithium 552 synthesis amination 517 arylmetallic, coupling with aryl ate complexes 358 from organometallics 786 Halides, metal catalyzed and Fries rearrangement 676 Arylation, active methylene 808–809 and hydroboration 736 compounds 819 arylnitrenes 715 and organolithium reagents 751 and radicals 820 arylpalladium compounds, borates, alkyl migration 736 enantioselective 820 formation of biaryls 658 ethers with borane 932 structural variations 820 arylsilanes, from aryl cyanides Lewis acids and halogens 643 arylation, amides and 547 onium salts 358 sulfonamides 527 arylthiocyanates 512 atom transfer, and Free radical amines, chiral 787 arylzinc reagents 561 addition 896 and the Heck reaction 810, 812 arynes, and aromaticity 774 radicals 897 decarboxylative 755 and NMR 774 reactions 843 Friedel-Crafts 657 and nonaromatic rings 774 radical 842 α−halocarbonyls 820 definition 773 atomic orbitals 8 intramolecular 880 hydrometallation 939 overlap of 5 lactams 529 in Diels-Alder reaction 774 atomization, heat of 29 See also Meerwein 830 Pauling resonance energy, heat of atomization metal catalysts 788 valence bond 774 atoms, chiral see chiral, N, amides and lactams 529 Pauling resonance order 774 stereogenic N, sulfonamides 529 regioselectivity in formation atoms, stereogenic see arylation, of active methylene 778 stereogenic, chiral compounds 820 substrate structure and atropic, annulenes 87 of alkenes, flow reactions 831 substitution 778 atropisomerism, and thioamides mechanism 831 ASAP papers 1608 177 of amines 635 ascaridole 1056 biaryls 802 Buchwald-Hartwig Cross ascorbic acid, and Udenfriend’s hydroxyalkylation of aromatic Coupling Reaction 786 reagent 865 compounds 653 flow reactions 786 association, of organolithium atropisomers, alkaloids 143 in ionic liquids 786 reagents 749 and a chiral axis 152 intramolecular 786 asymmetric see enantioselective and alkaloids 143 metal catalyzed 786–787 asymmetric, alkene isomerization and allenes 144 arylation, of arenediazonium salts 909 and benzylic alcohols 143 832 amination, of ketones 714 and BINAP 143 and radicals 832 boranes 935 and calixarenes 144 mechanism 832 catalysis 310, 312 and conformations 194 arylation, of aromatic compounds catalytic hydrogenation 1543 and metal complexes 143 657 dihydroxylation 1008 and restricted rotation 143 of aziridines 574 dihydroxylation, Sharpless and spiranes 144 of enolate anions 820 1008 biaryls 141–142 of heteroaryls 801 hydrogen bonds 109 biphenyls 142 of ketones 819 hydrogen transfer, Hantzsch colchicinoid alkaloids 143 and palladium catalysts 819 ester 1544 energy barrier to rotation 143 of silanes, metal catalyzed 822 hydrogen transfer, metal equilibrium constants 143 arylation, radical reactions 800 catalysts 1544 isolation of 143 radical, of aromatic compounds induction 165 pyrroles 143 879 Kumada coupling 807 sulfoxides 143 reactions, preparation with Nazarov 958 attacking reagent, definition 279 sonochemistry 333 Piers hydrosilation 1545 Austin model 36 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1944 SUBJECT INDEX

autoxidation, allylic and benzylic aza-Michael reaction 975 azides, acyl 532, 1336 hydrogens 867 DBU catalyzed 976 and the Curtius rearrangement and aldehydes 867 enantioselective 976 1371 and antioxidants 867 green 976 [3+2]-cycloaddition 1029 and oxidation of cathecols and lipase catalyzed 976 azides, acyl, decomposition 1336 hydroquinones 1460 metal catalyzed 976 from aldehydes 532, 1250 and oxygen 867 organocatalytss 976 from nitrous acid and and radicals 868 TEMPO catalyzed 976 hydrazines 1371 and singlet oxygen 869 aza-Payne rearrangement 498 thermolysis to isocyanates diketones 1466 aza-Peterson alkenylation 1192 1371 formation of hydroperoxides aza-Piancatelli rearrangement 959 azides, addition to alkenes 1021 867 aza-Pinacol reaction 1596 azides, alkyl, 1,3-dipolar addition initiation steps with oxygen aza-Prins cyclization 1215 1022 868 aza-Prins reaction 1215 acid catalyzed ring expansion mechanism 868 aza-Rauhut–Currier reaction 1445 1372 sulfonic acids, by oxidation of aza-Sakurai reactions 967 addition to alkenes 1022 thiols 1505 aza-Wacker process 1501 by Mitsunobu reaction, with auxiliaries, chiral see chiral aza-Wittig reaction 1202 alcohols 1374 auxiliary aza-Wittig rearrangement 1385 from alcohols, alkenes, and auxiliaries, Chiral, and Diels-Alder azaacepentalenide anion 92 hydrazoic acid 1374 reactions 1040 azaadamantane N-oxyls 1463 hydrazoic acid to Michael-type auxochrome 318 azaadamantanone, and strain 213 alkenes 931 awareness services 1624 and Wittig reaction 213 metal catalyzed Schmidt axial, in chair conformations 195 azaallyl anions 1308 reaction 1373 axis, chiral, and alkylidene azaannulenes 79 pyrolysis to imines 1372 cyclohexanes 152 azabicycles, and aza-Prins rearrangement 1378 and annulenes 152 reaction 1215 with conjugated alkenes 1023 and atropisomers 151 azabicyclo compounds 138 azides, and formation of nitrenes and cycloalkenes 152 azacalixarenes 119 276 and cyclophanes 152 azacrown ethers 118 and Mukaiyama reagent 532 and helicenes 152 photoisomerization 329 and the Staudinger reaction and metallocenes 152 azadicarbonyl dimorpholide, a 1565 and molecular gears 152 Mitsunobu reagent 500 and triazenes 741 and molecular propellers 152 azadienes, Diels-Alder reaction azides, arene 532 and R/S nomenclature 151 1053–1054 azides, aryl, ring expansion 1372 of symmetry 136 Povarov reaction 1054 with aryl azides 788 of symmetry, and chirality 136 with ketones 1055 azides, carbonylation 764 axle, molecular 130 azaferrocene, catalyst 1364 azides, from alcohols 531 aza-Baylis-Hillman reaction 1150 azapentadienyl cations 1392 from alkyl halides 531 and DABCO 1166 conversion to pyrroles 1392 from hydrazines 761 and imines 1166 Azeotrope Data 1621 azides, halo, by addition of and imines, enantioselectivity azeotropes, removal of water haloazide to alkenes 1002 1166 1112 reduction 1003 formation of amines, azeotropic distillation, and acetal with alkenes 1002 enantioselectivity 1166 formation 1101 with allenes 1002 aza-benzoin reaction 1216 and acetal or ketal formation azides, iodide, with alkynes 1003 aza-Bergman cyclization 1395 1101 azides, metal catalyzed reaction aza-Brook rearrangement 1437 and esterification of acids 1229 with epoxides 523 aza-Claisen rearrangement 1418 and formation of imines 1112 oxidation to nitriles 1503 enantioselectivity 1418 azetidines, by [2+2]-cycloaddition azides, reduction 525, 741 aza-Cope elimination 1308 1058 to amines, reagents 1564 aza-Cope rearrangement 1409, from amino halides 515 metals 1564 1418 from lactams 1195 azides, sodium, with aldehydes and the trichloroacetimidate from β-lactams 1549 1250 1418 with organometallics reagents azides, sulfonyl, and diazo-transfer enantioselectivity 1410 574 reactions 713 kinetic resolution 1409 azetidinium ylid, strained, reduction to sulfonamides 1565 aza-Darzens condensation 1191 epoxidation 1206 with active methylene aza-Diels-Alder reactions 1053 azide ions, and inversion 419 compounds 713 in ionic liquids 1053 and rate of ionization 419 with amides 713 aza-ene reaction see ene reaction with epoxides 523 azides, tosyl, with organolithium aza-Friedel-Crafts acylation 663 with epoxides, Mitsunobu 523 reagents 741 aza-Henry reaction 1186 azide, as a leaving group 741 vinyl, thermolysis 1023 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1945

with alkyl halides 531 diazo compounds, metal dienophiles 1053 with alkynes 1031, 1033 catalyzed 1167 E/Z isomers 329 with allenes 1031 from iodo azides 1003 from anilines 829, 1461 with CO 764 from photolysis of triazolines from aryl nitroso compounds with organometallics 741 1022 829 azidination, of amides 713 from sultams 1332 from azoxy compounds 1436, azido alcohols 523 from the aza-Darzans reaction 1586 azidoiodinane reagent 532 1191 isomerization, E/Z 638 azines, from aldehydes and aziridines, metal catalyzed loss of nitrogen 1462 ketones 1116 conversion to amines 1318 photoisomerization 329 azinic acids 102 photochemical cleavage 262 radical initiator 841 azirenes, and the Neber preparation, and flow reactions reduction to amines 1565, 1592 rearrangement 1369 526 regioselectivity of substitution intermediate in the Neber reaction with organosilanes 526 638 rearrangement 294 reaction with thiols 526 water soluble 841 aziridination, and ring expansion reduction 1584 azobenzenes, by reduction of nitro of aromatic compounds ring opening with metal compounds 1561 1024 catalysts 498 from aromatic nitro compounds of alkenes, enantioselectivity via nucleophilic substitution 1560 1024 447 isomerization 910 of alkenes, in ionic liquids via tellurium ylids 1207 reduction to hydrazobenzenes 1024 vinyl, [1,5]-hydrogen shifts 1555 of alkenes, organocatalysts 1403 2,2′-azobenzothiazole 512 1024 with alcohols 498 azobis compounds, radical of imines 1207 and Montmorillonite clay initiators 970 aziridines 139, 444 574 azobis(isobutyronitrile) see AIBN acyl, rearrangement 1408 with aldehydes 498 azodicarboxylate, diethyl see ambident substrates 482 with alkynes 1033 DEAD and chiral ammonium salt 1023 with amines 525 azodicarboxylates 500 and Chloramine-T 1023 with boronates 594 azo dyes, by diazonium coupling and leaving groups 465 with carbon dioxide 765 638 and radicals 1024 with carbon monoxide 1264 azomethine imines, and the tetrahedral mechanism with diselenides 575 [3+2]-cycloaddition 1030 447 with nitrous acid 1318 azonine 78 arylation 574 with nucleophiles 575 azoxy compounds 762 asymmetric, from alkenes 1024 with organolithium reagents acid catalyzed rearrangement to by extrusion of nitrogen from 1034 azo compounds 1436 triazolines 1330 with organometallics reagents and ESR 763 by flow reactions 1024 574 and radicals 763 by reduction of oximes 1563 aziridinium salts, and migration of and the Wallach rearrangement by SN2 reaction 519 amino groups 1367 1436 by thermolysis of triazolines cleavage 542 by oxidation of amines 1462 1022 from amine–halides 1367 by oxidation of amines 1462 chiral 532 with water 1367 by reduction of nitro from reduction of azirines azirines 1023 compounds, reagents 1024 as with water 1369 1600 cleavage 542 azo compounds 710, 1053 [3+2]-cycloaddition 1030 conformational stability 139 See also AIBN from alkyl halides 534 conversion to alkenes 1318 azo compounds, and E/Z from nitroso compounds 762 conversion to imines 1461 nomenclature 177 from oximes 762 enantioselective ring opening and radicals 262 reduction to amines 1592 498 and the Mills reaction 829 to azo compounds 1586 from alkenes 1022 aryl, from aryl triazenes 679 to azo compounds, reagents and chloramine-T 1024 by oxidation of amines or 1586 from β-amino alcohols 519 anilines 1462 to azo compounds, reagents from amino halides 515 by reduction of azoxy 1586 from diazoacetates and imines compounds, reagents 1586 with hydride reagents 1586 1022 by reduction of nitro azoxyalkanes, from from epoxides 524 compounds, reagents 1600 alkanediazotates 533 from haloamines 515 by Wallach rearrangement azoxybenzenes, by reduction of from imines 1207 1436 nitro compounds 1561 and diazo compounds 1167 azo compounds, decomposition to from aromatic nitro compounds and sulfur ylids 1207 radicals 840–841 1560 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1946 SUBJECT INDEX

azulene, and aromaticity 67 conjugated alkenes 1530 hydrolysis 383 and carbocations 229 reduction of aldehydes or rearrangement, O-tosyl imines and fluorescence 322 ketones 1541 to amino ketones 1369 and MO calculations 67 reduction of azides 1564 base induced, addition of amides dianion 68 reduction of oximes 1562 to aldehydes 1122 dipole moment 68 Baldwin’s rules for ring closure deprotonation, aldehydes or non-alternant hydrocarbon 69 288–289, 948 ketones 703 radical cations 266 enolate anions 289 elimination of alkyl halides stability 68 and radical cyclization 971 1311 azulenyl nitrones, and radicals ball milling, and oxidative base strength 340 252 amidation 873 and E2C reactions 1287 and reactions 338 and field effects 362 B strain see strain hydrazines, with aldehydes or and hydrogen bonding 347 B-alkycatecholboranes, radical ketones 1116 and pK, table 348 initiators 842 oxidation of amines 1504 and proton sponges 367 B-halodiisopinocampheylboranes, preparation of nitrones 1504 and solvent effects 349 chiral cleavage of ethers Suzuki-Miyaura coupling 800 superbases 349 541 Balz-Schiemann reaction see table 366 B2(Pin)2, with alkynes 936 Schiemann reaction base-catalyzed acylation of B to O rearrangement 1385 Bamberger rearrangement 836 alcohols 1227 Bacillus megaterium 668 mechanism 836 reactions 356 allylic compound oxidation Bamford-Stevens reaction 1309 base-induced elimination 1274 1480 and flow reactions 713 of ethers 1301 benzylic compound oxidation formation of diazo compounds bases, amide see amide bases 1480 1310 bases, alkenes 349 back donation and mechanism 1310 alkoxide, with halo esters 1190 oxymercuration 913 solvent effects 1309 amide 515 Pauson-Khand reaction, suitable bases 1309 amidinazines 349 mechanism 987 banana bonds, and cyclopropane and active methylene backside attack, and SN2 404, 688 209 compounds 575 and substitution 404 barbaralane, and Cope and arenium ion isotope effects Bader’s electron delocalization rearrangement 1413 610 index 64 Barbier reaction 1130 and formation of phosphorus Baeyer strain 207 and metal catalyst 1130 ylids 1194 Baeyer-Villiger rearrangement and organolithium reagents and haloform reaction 757 1378 1134 and hydrogen exchange, and buffers 1379 and the Grignard reaction 1130 aromatic substitution and epoxidation 1016 retro- 1130 630 and polymer-supported peroxy with aldehydes or ketones 1136 and keto-enol tautomerism 701 acids 1379 Barbier-Wieland procedure, and pK, table 348 and the Dakin reaction 1473 oxidative cleavage of and the Stetter reaction 981 anti-, versus gauche migration alkenes 1471 as proton acceptor 339 1379 barbituric acid 1249 bases, base strength 347 aryl migration 1380 barrelene 88 and solvents 349 enantioselectivity 1379 and chirality 146 table 366 ionic liquids 1378 barrier, energy, to rotation 178 bases, catalysis, of amine isotope effects 1380 intrinsic 292 substitution of aryl halides mechanism 1379–1380 rotation, biphenyls 141 769 metal catalysts 1378, 1671 rotation, in acetaldehyde 193 bases, cleavage of diketones 757 migratory aptitude 1379 Barton decarboxylation, and of keto esters 757 organocatalysts 1379 ultrasonic flow reactions of ketones, steric effects 758 solvent free 1379 755 bases, conjugate 339 Baird’s theory 68 Barton reaction 1434 dialkylamides 369 Baker-Nathan effect, and and nitroso compounds 1434 bases, enolate anions 369 hyperconjugation 93–94 and steroids 1434 for deprotonation of carbonyl and substitution reactions 455 mechanism 1434 compounds 579 SEAr 618 Barton-McCombie reaction 1576 of the Henry reaction 1185 Baker’s yeast, and reduction of base catalysis 356 organolithium reagents 350 nitro compounds 1560 base catalyzed, and arenium ion organometallics 350 enantioselective reduction of partition factor 610 pKa and deprotonation 575 alkenes 1521 and the Marcus equation 356 proton sponges 349, 367 enantioselective reduction of hydration of aldehydes and proton-transfer reactions 350 alkynes 1521 ketones 1096 quinilino-quinolines 349 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1947

reaction with phosphonium and poly(ethylene glycol) 1150 benzene rings, and strain 220 salts 1194 and Rauhut-Currier cyclization bonds, and cyclopropane 209 required for generation of 1151 benz(h)isoquinoline 1616 enolate anions 579 and sulfolanes 1150 benzaldehyde lyase from Schwesinger proton sponges and ultrasound 1150 Pseudomonas fluorescens 349 aza- 1150 catalyst 1216 soft, definition 359 double 1166 benzamides, carbaldehyde 103 softness 359 double bond isomerization hydrolysis 1093 solvents 353 1152 iodination 646 strength 340 enantioselectivity 1151 benzanthracenes 50 and structure 361 functional group compatibility benzene oxide, from oxepin 1414 and the Claisen condensation 1151 benzene-1,3,5-triyl triformate, CO 1255 in aqueous media 1150 source 670 suitable for the Sevens intramolecular 1151 benzene, and bond order 35 rearrangement 1381 ionic liquids 1151 and carbocations 608 superbases 349 lactonization 1152 and delocalization 39 and transesterification 1233 mechanism 1150 and HMO theory 38 vinamidine type 349 metal mediated 1151 and metal complexes 115 with ammonium salts 1307 organocatalysts 1150 and NMR 55 with dialkylamino halides 1321 proton catalyzed 1150 and planarity 50 with epoxide 1302 sila- 1150 and resonance 34 with esters 1417 vinylogous 1445 and ring current 55–56 with carboxylic esters 1183 9-BBN 934 and the aromatic sextet 54 basicity, amines 349 and conjugate addition 967 and the diene-cyclobutene and ambident nucleophiles 480 with alkenes 934 interconversion 1395 and differential hydration 371 Beckmann rearrangement 664, benzene, aromatic sextet 35 and electronegativity 365 1326, 1338–1369, 1375 aromaticity 39 and hydrogen bonding 106 abnormal 1326, 1369, 1377 bent 220 and ionic strength 373 and microwaves 1375 boat conformation 51 and leaving groups 465 and the Ritter reaction 1377 bond energy 37 and nucleophilicity 459 and the Schmidt rearrangement delocalization an MO 37 and proton affinity 347 1376 delocalization and valence bond and resonance 366 formation of thioamides 1377 theory 37 and solvent effects 371 from oximes 1461 derivatives, cycloaddition 1312 and steric effects 366 in ionic liquids 1375 dimer 113 the medium 370 in supercritical water 1375 electrostatic potential map 34 basicity, electronic effects 366 ionic liquids 1376 from alkynes 1078 gas phase 371 mechanism 1376–1377 heat of atomization 37 hydrogen bond 347 migratory aptitude 1376 heat of hydrogenation 38 in solution, of amines or migratory aptitudes of groups hexaisopropyl 219 ammonia 371 1341 molecular orbitals 35 in THF and water 349 polymer bound 1375 orientation in substitution 614 pyridines 367, 372 reagents for 1375 reactivity 614 pyrrole 372 second order 1326 relative aromaticity 39 pyrrole versus pyridine 63 solvent free 1376 resonance energy 38, 60 solution versus gas phase 371 stereochemistry of migrating rings, from dienes 1437 table 348 groups 1338 nonplanar 50 basis sets, molecular orbitals 1048 Beilstein 1617, 1630–1631 strained 51 transition state, Beilstein CrossFire, replaced by structure 33–34 [2+2]-cyclizations 1049 Reaxys 1619 substituted, UV, table 318 transition state, Beilstein, Ergzanzungswerks¨ benzene, tri-tert-butyl 218 [4+2]-cyclizations 1049 1618 benzenechromium tricarbonyl bathochromic shift 318 Beilstein, Handbuch der 115 bay region, phenanthrene 60 Organischen Chemie 1617 benzeneseleninic anhydride 716 Bayer test, and dihydroxylation of organization 1618 benzenoid hydrocarbons, and alkenes 1006 organization, table 1618 aromaticity 57 Baylis-Hillman carbonates 1151 supplements 1618 benzenoid polyaromatic Baylis-Hillman reaction 1149 Bell–Evans–Polanyi principle, and compounds 58 and alkene carbonylation 985 activation energy 620 benzenonium ion 611 and chiral auxiliaries 1151 belts, cyclophanes 50 and chemical shift 611 and DABCO 1149 molecular 128 and NMR 611 and ionic liquids 1150 Benkeser reduction 1526 electron potential map 611 and microwaves 1150 bent alkynes 901 spectral analysis 611 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1948 SUBJECT INDEX

benzhydrol, reduction to benzoyl peroxide 853 Grignard reagents, with aryl benzpinacol 330 homolytic cleavage 840 halides 805 benzidine rearrangement 1422 photochemical cleavage 263 reactivity order of halides 773 and [3,3]-sigmatropic benzoyl radicals 263 benzynes, reactions, and field rearrangement 1424 benzoylnorephedrine, and effects 778 and [5,5]-sigmatropic rearrangement 379 regioselectivity 773 rearrangement 1424 benzpinacol, from benzhydrol Truce-Smiles rearrangement disproportionation 1423 330 838 isotope labeling 1423 benzvalene 49, 1414 Bergman cyclization 1395, 1412 kinetics 1422 benzyl carbanion, energy levels and diradicals 1395 mechanism 1422 70 aza- 1395 non-concerted 1424 benzyl carbocations 230 betaines 1196 rate determining step 1423 benzyl cation, energy levels 70 conversion to alkenes, benzil 1361 benzyl chloroformate see stereochemistry 1200 benzil-benzylic acid chloroformate mechanism, Wittig reaction rearrangement 1361 benzyl radical, energy levels 70 1196 mechanism 1361 benzylic carbanions 239 X-ray 1197 benzoannulenes, and aromaticity canonical forms 240 betweenanenes, and strain 216 83 benzylic carbocations 228 bi-tert-butylperoxide, homolytic benzocorannulenes 92 forms 228 cleavage 840 benzocyclobutane 26 benzylic CH oxidation 1478 biadamantylidene 214 derivatives, and bond distance benzylic compound oxidation, and biaryls, and atropisomerism 802 26 Bacillus megaterium 1480 and atropisomers 141 benzocyclobutenes 51 and ultrasound 1479 and Birch reduction 1525 by extrusion of sulfur dioxide benzylic compounds, and and Cahn-Ingold-Prelog system 1331 autoxidation 867 152 electrocyclic ring opening and Etard´ reaction 1478 and chirality 141 1389 benzylic halogenation, radical and hydroxylation of aromatic ring current 52 862 compounds 865 benzocyclohepatrienyl anion 77 benzylic hydrogenation, with and metal catalysts 795 benzocyclopropene 51 radicals 852 and symmetry 141–142 and strain 215–216 benzylic oxidation aldehydes, aryl, and the Gatterman method 833 benzodehydro[12]annulene 86 reagents 1478–1480 arenium ion mechanism 810 benzofurans, metal catalyzed aerobic 1480 by nucleophilic substitution cleavage 571 benzylic radicals 852 796 benzoic acids, field effects 363 benzylic substrates, and SN2 rate by the Gomberg reaction 831 from arenes 1480 of reaction 452 by the Scholl reaction 657 pKa 363 and substitution reactions 452 chiral 802 substituent effects 363 benzyloxylation, allylic 1482 conformations 195 substituents and pKa 363 benzyltrimethylammonium, coupling or aryldiazonium salts with arenediazonium salts 832 rearrangement 1383 with aromatic compounds benzoin condensation 1215 benzynes 772 831 and acyloins 1216 and aromaticity 774 diamino, by benzidine and addition of HCN to and arynes 773 rearrangement 1422 carbonyls 1210 and Diels-Alder reactions 1041 from hydrazobenzene 1422 and benzaldehyde lyase 1216 and Fischer indoles synthesis dimerization of aryldiazonium and thiazolium salts catalyst 1420 salts 833 1216 and Suzuki-Miyaura coupling for aryl organometallics 657 enantioselectivity 1216 803 biaryls, from aromatic compounds mechanism 1216 and the Diels-Alder reaction 879 mixed 1217 295 from aryl halides 879 N-heterocyclic carbene as intermediates 295 and arylboronic acids 798 catalysts 1216 click reaction, photoinduced from aryl radicals 845 benzoins see hydroxy-ketones 774 from aryldiazonium salts 833 benzoins 1215 definition 772 from organometallics and aryl benzophenone, and cross formation, reactivity of halides halides 795 conjugation 44 773 biaryls, metal catalyzed coupling benzoquinone, radical inhibitor fused ring 774 of Grignard reagents 881 844 isolation 774 metalated aryl and aromatic benzotriazoles 656 benzynes, mechanism 295, 772, compounds 657 benzoxazine, tautomerism 103 777, 1284 of heteroaromatic compounds benzoxazoles, amination 636 and cine substitution 773 658 benzoyl formate, methyl 164 and isotope labeling 772 preparation via biocatalysis 799 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1949

synthesis metal free 800 biphasic system, and Williamson bis(thocyanato)alkenes 999 with microwaves 798 ether synthesis 490 biscalixarenes 128 unsymmetrical 796 biphenyl, activation energy of Bischler-Napieralski reaction, via coupling of aryl halides 797 rotation 141 dihydroisoquinolines 655 via Suzuki-Miyaura coupling and complex formation 122 Friedel-Crafts cyclization 655 798 biphenylene, isomerization 1399 bisdithiocarbonates, conversion to via Ullmann reaction 797 quinones 77 alkenes 1315 bicarbenes 269 biphenylenediol, and hydrogen bisecting bonds, and bicyclic alkenes, and Bredt’s rule bonds 108 conformations 192 217 biphenylenes, pyrolysis and bisecting conformation 194 from dienes 943 diradicals 1399 bishomoaromatic 91 bicyclic bridged compounds 181 biphenyls, and atropisomers 142 bisimidazolium compounds 132 bicyclic cations 111 and chirality 141 bismuth compounds, and acetal bicyclic compounds, and Bredt’s and isomerization 685 cleavage 488 rule 752 barrier to rotation 190 bisoxazoline ligands 715 and SN1 reactions 413 rotation barrier 141 bisulfite addition products 1111 decarboxylation 752 biradicals see diradicals with cyanide 1211 bicyclo[2.2.2]octylidene 268 Birch reduction 265, 1520 bisulfite, sodium see sodium bicyclobutanes, conversion to and alkenes 1525 bisulfite dienes 1431 and electron transfer 1441 Blaise reaction 1153, 1169 from dienes 1431 and NMR 1525–1526 organozinc reagents, with bicyclobutonium ion 438 and principle of least motion nitriles 1169 bicycloheptadienes, 1525 bmim, ionic liquids 394 photochemistry 329 aromatic compounds 1524 boat conformation 195 Dewar formula 1063 mechanism 1525 and benzene 51 bicyclopropyl molecules 1431 2,4-bis(4-methoxyphenyl)-1,3,2,4- cycloheptatriene cations 65 bifluorenylidene, rearrangement dithiadiphosphetane-2,4- Bobbitt’s reagent, and oxidation of 1399 disulfide see Lawesson’s alcohols 1452 bifurcated hydrogen bonds 108 reagent Boekelheide reaction 1383 Bijvoet, and X-ray analysis 149 bis(alkoxides) 1598 boiling point, and Beilstein 1618 bimetallic compounds 951 metal mediated formation of and hydrogen bonding 110 bimolecular substitution 688 alkenes 1315 and transesterification 1233 See also substitution, SN2 bis(amides), from addition of elevation, and Grignard BINAP, and atropisomers 143 amides to aldehydes 1122 reagents 246 binapthols, chiral 168 from hydroxyamides 1122 bond alternation 86 BINOL, and formation of bis(amino)fluorenes, as proton and phenylenes 51 amino-alcohols 523 sponges 367 annulenes 87 and the Pictet-Spengler reaction bis(amino)naphthalenes, as proton pentalene derivatives 67 655 sponges 367 tropone and tropolone 65 bio-epoxidation 1016 bis(amino)phenanthrenes, as bond angles 27 See also angle biocatalysts 310 proton sponges 367 and alkanes 27 aldol condensation 1177 bis(decarboxylation), of and alkyl halides 27 amides, from esters 1246 dicarboxylic acids 1475 and annulenes 78 and thio-Michael addition 978 of dicarboxylic acids, and carbenes 268 carbonyls with cyanide 1210 mechanism 1475 and carbocations 378 for biaryl preparation 799 bis(dimethylamino)naphthalene, and carbon tetrachloride 27 Henry reaction 1186 proton sponge 349 and conformation 202 ketones, with HCN 1210 2,2′-bis(diphenylphosphino)-1,1′- and E2 reactions 1277 magnetic nonabeads 311 binaphthyl see BINAP and hybridization 27 reduction of aldehydes or bis(oxazoline) copper catalyst 962 and ionization of alkyl halides ketones 1542–1543 bis(phosphines), and chiral ligands 378 [2,3]-sigmatropic in catalytic hydrogenation and lone pairs 28 rearrangements, 1515 and orbitals 27 biocatalysts 1421 bis(phosphoranes), and out–in and p character 28 thio-Michael addition 978 isomers 183 and radical hydrogen biochemical deracemization 172 bis(pinacolato)diboron 934 abstraction 1023 biomimetic epoxidation 1013 bis(quaternary)ammonium salts and resonance 48 biomimetic Heck reaction 814 475 and s character 28 biooxidation, and catalytic bis(selenenyl) compounds, from and stability 48 dehydrogenation 1455 alkenes 1018 and strained molecules 28 biosynthesis, cholesterol 944 bis(tetramethylguanidino) bromoalkanes 27 squalene to lanostereol 944 naphthalene, proton cyclooctatetraene 77 steroids 944 sponge 349 in ethylene 10 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1950 SUBJECT INDEX

bond angles (Continued) sp3 carbon compounds, table of naphthalene 59 in organic compounds, table 28 25–26 ring 64 methane 9 table 24, 26 σ-bond participation, and MO calculations 37 bond elongation, and cyclopropylmethyl groups O and N containing compounds, hyperconjugation 95 436 table 28 bond energy 17, 29, 105 bond polarization 17 See also O, S, N compounds 28 and atom abstraction by polarization of BF3 9 radicals 849 bond resonance energy 64 of nitrogen 7 and bond distance 31 bond rotation, and carbenes 267 of oxygen 7 and bond length 32 and E2 reaction 1278 of water 7 and bond type 32 and kinetics 303 solvent effects 7 and dissociation energy 29 in radicals 260 table 24, 28 and double bonds 32 restricted 177 bond cleavage, and mechanism and electronegativity 17, 30 bond strength, and periodic table 279 and electronic effects 32 31 dissociate states 319 and heat of atomization 29 bond switching, and the heterolytic 279 and heat of combustion 29 Stone-Wales bond dissociation energy see and hybridization 30, 32 rearrangement 1399 energy and hydrogen bonding 31 bond type 18 bond dissociation energy, and and ionic configuration 31–32 and bond distance 26 hyperconjugation 94 and keto-enol tautomerism and bond energy 31–32 and radical halogenation 97 bonding electrons 33 860 and orbital interactions 32 bonding orbitals 5 C—H, and radical reactivity and Pauli repulsion 32 allylic carbocation 42 849 and radicals 32 bonding, and tautomerism 97 C—D bond 304 and ring strain 32 charge-transfer 117, 119 HX, table 861 and s character 30, 32 covalent 3 radicals and reactivity 855 and solvents 32 delocalized 33 bond distance 23 and steric factors 30 dipole induced 119 and annulenes 83 and the periodic table 32 in ferrocene 66–67 and antiaromaticity 57 bond energy, benzene 37 in metallocenes 66 and aromaticity 71 bond types 30 localized chemical 3 and benzocyclobutane cyclohexene 37 maximum coordination number derivatives 26 hydrocarbons 30 9 and benzocylobutene 52 hydrogen bonds 106 multicenter 112 and bond energy 31 in diatomic molecules 29 π−bonding, second row and bond type, table 26 isobutane 30 elements 12 and cross conjugation 45 isopentane 30 P-P 183 and delocalization 39, 56 methane 30 σ-bonds, rearrangements, metal and electron diffraction 24 of organic compounds 32 catalyzed 1431 and fused aromatic compounds propane 30 rearrangements, metal 60 solvent effects 31 catalyzed, mechanism and hybridization 26 bond fixation 74 1431 and hyperconjugation 49, 94 and PES 74 migration, and dyotropic and microwave spectroscopy in aromatic rings 60 rearrangement 1437 24 phenanthrene 60 bonds, and π-bond distance 26 and molecular mechanics bond length see bond distance electronic structure 16 204 bond length 49 and formal charge 17 and orbitals 26 bond length, and bond energy 32 and Fukui function 891 and resonance 48 and s character 31 and π resonance 47 and s character 26, 452 annulenes 81 and σ+ρ-resonance 34 and spectroscopy 24 cycloheptatrienide anion 77 annelated 52 and stability 48 σ-bond migration, and sigmatropic as σ-neighboring groups 433 and strain 220 rearrangement 1400 banana, and cyclopropane 209 and X-ray 26 Favorskii rearrangement 1362 bent, and cyclopropane 209 and X-ray diffraction 23 bond moments 19 C—Si 12 and π-bonds 26 bond order, and aromaticity 56 C—D, bond dissociation energy annulenes 80, 87 and cross conjugation 44 304 aromatic rings 41 and aromaticity index 64 C≡N triple bond 11 C–D 26 and benzene 35 C=S 12 C—Si 24 and NMR 60 coordinate covalent 17 bridged compounds 221 and resonance 33 delocalized 41 MO calculations 37 cyclopentadienide ion 64 double bond in ethylene 9–10 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1951

double bond to O or N 11 chiral 935 boranes, with alkenes 735, 932, double bonds to S, O, Si 12 chiral boranes 935 1314 energy and wavelength 319 with aldehydes and silyl enol with alkynes 1388 in fused ring aromatic ethers 1182 with carbon monoxide 1385 compounds 52 boranes, conjugate addition 967 with chiral additives, and in ylids 52 and galvinoxyl 969 reduction 1544 ionic, and electronegativity 19 and oxygen 967 with CO 1387 long bonds 26 and peroxide 967 with diazo compounds 593 metallocenes 116 enantioselective 967 with esters 1158 multiple 9, 12 metal catalyst 967 with halo esters 593 multiple, and PES 15 NHC catalyst 967 with halo nitriles 593 neighboring group, conversion to alcohols 1387 with halogens 740 π-participation 425 conversion to aldehydes 1387 with halomethyl ethers 1386 neighboring group conversion to amines 928 with hydrogen peroxide 1385 σ-participation 425 cyano see cyanoboranes with imines, radicals 1165 bonds, nonadjacent, stabilization dimers 933 with iodine and NaOH 1388 of π-carbanions 242 elimination to alkenes 1314 with lactams 1160 organometallic 244 and Zaitsev’s rule 1314 with metals 967 PES and methane 14 equilibrium 1314 with NBS or NCS 740 polar-covalent, and enol 164 borates 735 organometallics 244 fluorination 740 and Stille coupling 719 polarized 17 boranes, from borane with alkenes, by borylation of boranes 736 Si=Si double bond 12 mechanism 736 by oxidation of boranes 736 triple 11 from boranes 1368 by reduction of aldehydes or triple bond in ethyne 11 from Grignard reagents 744 ketones with boranes π-bonds 26 isomerization 1368 1539 Boord reaction 1320 equilibrium 1368 conjugate addition 968 metal catalysts 1321 migration of boron 1368 conversion to esters 606 with Grignard reagents 1321 of boron, mechanism 1368 enol 1176 bora(9-)bicyclo[3.3.1]nonane see optically active 1146 from alcohols 737 9-BBN order of reactivity 841 from aryl halides 792 boranes-N-heterocyclic carbenes oxidation to borates 736 from boranes 1385 1554 and boron–carbon hydrolysis to alcohols 1539 boranes-THF, reaction with rearrangement 1385 preparation 735 alkenes 933 mechanism 1385 borderline mechanism, and boranes, addition to alkenes, steric boranes, protonolysis with substitution 419 effects 933 carboxylic acids 1522 borderline SN2 reactions 418 alkenyl, from alkynes 1388 radical initiators 841, 970 boric acid catalyst 1249 with NaOH and iodine 1388 reagents for reduction 1539 boric acid-amino acids, and boranes, alkyl, coupling, silver reduction 1387 resolution 167 catalyzed 882 of aldehydes or ketones boric anhydride, and boranes, alkylation 592 1539 decarboxylation 754 of bromoketones 592 of azo compounds 1592 borinates, enol 1174 mechanism 593 of carboxylic acids 1547 from conjugate addition of metal catalyst 593 of carboxylic acids, metal boranes 967 boranes, allylic, and acyl addition catalysts 1547 hydrolysis 967 1145 enantioselectivity 1540 Borodin, Alexander 886 with epoxides 573 boranes, thermal isomerization borohydride exchange resin, and boranes, and alkyne formation 1314 reduction of alkynes 1522 1314 thermolysis 1368 and reduction of nitro and alkynes, reduction to boranes, vinyl see boranes, compounds 1560 alkenes 1522 alkenyl borohydride, nickel, with and anti-Markovnikov addition boranes, vinyl, coupling with alkyl thiophenes 884 933 halides 593 borohydride, sodium see sodium and chain elongation 967 dimerization 883 borohydride and ether solvents 933 from alkynes 936 borohydride, sodium, and and radical cyclization 969 oxidation with peroxide to give reduction of acyl halides and radicals 969 ketones 1388 1580 boranes, and trifluoroacetic with halogens 740 and reduction of imines 1553 anhydride 1387 with iodide and hydroxide 1388 functional group reactivity aryl, from aryl halides 792 boranes, with aldehydes, 1533 asymmetric 935 enantoselectivity 1146 reduction of conjugated ate complexes with ethers 932 metal catalyzed 1146 carbonyls 1533 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1952 SUBJECT INDEX

borohydride, sodium, and and Stille coupling 719 with imines, metal catalyzed reduction of acyl halides and Suzuki-Miyara coupling 1165 (Continued) 593–594 with nitriles, metal catalysts with chiral additives 1544 boronic acids, aryl, and 1169 with Lewis acids, reduction of Friedel-Crafts alkylation with thiols 784 ethers 1579 650 with triflates 593 boroles, radical initiator 842 and Grignard reagents 735 with aldehydes, metal catalyzed boron compounds, aryl, from aryl and the Suzuki-Miyaura 1147 halides 792 reaction 735 boronic esters, alkenyl 737 radical imitator 841 conversion to amides 669 aryl, with carbon dioxide and boron reagents, hydroxyalkylation coupling with arylmetallic, metal catalyst 668 653 metal catalyzed 808–809 aryl, with carbon monoxide and boron trichloride, preparation of with heteroaryl substrates metal catalyst 668 borates 737 801 chemoselective 802 and conjugate addition of homocoupling 799 conversion to amides 743 boranes to alkyne–ketones iodination 646 conversion to conjugated 969 metal catalyzed addition to carboxylic esters 743 and conversion of alkenes to alkynes 951 coupling with aryl halides alcohols 483 nitration 631 804 and orbitals 9 substrates for coupling 801 cyclotrimerization 1077 electronic structure 17 with alkenes, metal catalysis from trifluoroborates 793 with amines, and amides 1247 803 with amides 594 boron-to-carbon rearrangement with alkynes 951 with organolithium reagents 1385 with aryl halides 798 595 boron-Wittig reaction 1202 with halocarbonyls 820 borosilanes 967 boronate esters, conjugate with sulfonyl halides 1271 boroxinate catalyst 1208 addition 968 boronic acids, carbonylation 605 boroxines, aryl, with amines from alkenes 937 with conjugated ketones 988 636 from hydroboration of alkenes boronic acids, catalysts 1242 preparation 735 736 for conversion of carboxylic borylation, metal catalyzed 792 stability 737 acids to amides 1242 bosons 134 boronates 593, 735 boronic acids, conjugate addition Bouveault reaction, and amides alkylation 592 968 1159 and Suzuki reaction, chiral boronic acids, conversion to Bouveault-Blanc procedure 737 aldehydes 1387 1537 aryl, by ipso substitution to aryl nitriles 795 reduction of esters to alcohols 793 to trifluoroborates 738 1548 from aryl halides 792–793 boronic acids, coupling with acyl bowl-shaped hydrocarbons 92 from organometallics, flow halides 804 bowl-to-bowl inversion 92 reactions 792 with alkyl halides 801 Boyland-Sims oxidation 674 heteroaryl, conjugated addition boronic acids, from Bradsher reaction, Friedel-Crafts 968 trifluoroborates 793 cyclization 654 metal catalyzed, preparation iodoaryl, polymer supported Bredt, anti-, alkenes 1196 792 1244 Bredt’s rule, and bicyclic alkenes oxidation 1387 methylation of amines 516 217 vinyl, and NHC catalysts 936 vinyl, coupling 801 and cyclic alkenes 217 with aziridines 594 boronic acids, with acyl halides and decarboxylation 752 with epoxides 594 1156 and elimination reactions 1288 with imines, enantioselectivity with alcohols 595 and enol formation 752 1165 with aldehydes, metal catalyzed definition 217 metal catalyzed 1165 1146 pyrolytic elimination 1298 with phenols 594 with alkynes 950 bridged annulenes see annulenes boron, electronic configuration 8 with anhydrides 1156 bridged carbocations 425 migration in organoboranes with aryldiazonium salts 801 bridged radicals 847 See also 1368 with carboxylic acids, metal radicals boronic acids 497, 735 catalyzed 1154 bridged systems, IUPAC names alkyl, metal-mediated coupling with cyanoacetates 724 210 559 with enynes 943 bridged tetradehydroannulene 83 alkylation 592 with epoxides 595 bridgehead alkenes 217 and bromomethyllithium 593 with hydride reagents reduction bridgehead atoms, and chirality and carbonylation of aryl of carboxylic acids 1547 139 halides 822 with hydrogen peroxide, gives bridgehead carbocations and flow reactions 736 phenols 780 232–234, 414 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1953

bridgehead carbons, and SN1 bromomethylithium, and boronic BSA, and the Tsuji-Trost reaction reactions 413, 691 acids 593 564 and SN2 reactions 406, 456 bromonium ions 897–898, 992 bubbles, and ultrasound 477 substitution 689 See also halonium Bucherer reaction 790 bridgehead diazonium ions and neighboring group Buchner¨ ring expansion 1070 639 mechanism 423 Buchwald-Hartwig Cross bridgehead hydrogens, reactivity radical 847 Coupling Reaction 786 with radicals 853 bromosaccharin 997 in water 787 bridgehead ions, large 233 bromothiocyanation 999–1000 ionic liquids 787 bridgehead keto-acids, Brønsted acidity, and Lewis mechanism 787 decarboxylation 752 acidity 366 microwaves 787 bridgehead radicals 260 increases, going down the SN(ANRORC) mechanism British Abstracts 1617 periodic table 366 787 bromamine-T 1504 Brønsted acids 340–347 SNAr mechanism 787 bromides, acyl see halides, acyl catalysts, [3+2]-cycloaddition buckminsterfullerene 91 alkyl, and Grignard reagents 1032 buckminsterfullerenes, semi- 92 247 chiral 1554 bucky bowls 91 alkyl, rates of solvolysis 450 as catalysts 508 inversion 92 bromination 858 enantioselective hydrolysis buckyballs 91 allylic 864 489 buffers, acetohydroxamate 1282 aromatic compounds 642 intramolecular cyclization and Baeyer-Villiger of alkenes, cyclic intermediate 492 rearrangement 1379 894 Brønsted bases 347–350 bullvalene 1414 reagent, 1,2- Brønsted catalysis equation 355 and Cope rearrangement 1412 dipyridiniumditribromide Brønsted coefficient, and acetal and NMR 1412 ethane 537 hydrolysis 487 tautomeric forms 1412 with NBS 863 Brønsted equation, and Bunnett-Olsen equation, and Wohl Ziegler reaction 863 equilibrium constants 356 solvent acidity 354 bromine, alkene reactivity, table and free energy 356 Bunte salts, formation of 899–900 and Marcus equation 356 disulfides 510 and acetone, and mechanism and mechanism 1288 from alkyl halides 510 304 Brønsted plot, and nucleophilicity hydrolysis 506 and cyclobutane 209 463 Burgess reagent, and dehydration and cyclopropane 208 and SN2 409 of amide to nitriles and Hell-Volhard-Zelenskii Brønsted relation 383 1327 reaction 708 Brønsted theory 339 and dehydration of oximes to and heptalene 67 Brønsted α term 356 nitriles 1325 and phenanthrene 60 Brønsted β term 356 and oxidation of alcohols cation 993 Brønsted-Lowry acids 308 1451 from NBS 864 and decarbonylation of aryl conversion of carboxylic acids radicals 263 aldehydes 683 to amides 1242 with alkenes 906, 1441 catalysts, Diels-Alder reaction structure 1325 and peroxide 1348 1037 butadiene–cyclobutene, and orbital solvent effects 899 rearrangement of N-nitroaniline symmetry 1396 substituent effects 900 677 butadiene, and cross conjugation with anthracene 60 Brook rearrangement 1437 44 with aromatic compounds 642 and dithianes 1110, 1438 and delocalization 39 bromine∙dioxane complex 645 and epoxides 1110 delocalization 41 bromite, sodium see sodium and HMPA 1438 electrostatic potential map 40 bromo-lactams 1001 aza- 1437 energy of 40 bromoacetophenone, with amines homo- 1437 heat of atomization 41 454 phosha- 1438 hybridization 41 bromoacids 147 reverse 1437–1438 molecular orbitals 40 bromoalkynes, with synthetic applications 1438 orbitals of 40 cyclopropanol 599 brosylates 465 resonance energy 40 bromoamine, with alkenes 1024 and solvolysis 416 butadiyne 42 bromocarbenium ions 994 leaving groups 465 butan-2-ol, enantiomers 134 bromocyclooctatetraene 77 solvolysis 427 butane, and conformations 190 bromocyclopropylidenoids 1319 Brown σ* values, electrophilic and gauche conformations 191 bromoform, flash photolysis 269 aromatic substitution 627 conformational energy 192 bromomethane, bond angles 27 brucine, and resolution 167 conformations 191 with KOH 1440 Bruylants reaction 568 derivatives, conformations with LiAlH4 1440 and iminium ions 568 192 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1954 SUBJECT INDEX

butanolides, from allene and chirality 147 caprolactams, conformation 203 carboxylic acids 921 enantiopure 120 captodative effect 74 and the Claisen rearrangement immobilized 119 and ESR 256 1417 resolution 167 and radicals 255 via the aza-Cope rearrangement calixazulene 119 and radicals 256 1418 calixcrown ethers 120 carbenes, and hindered alkenes butylated hydroxytoluene 889 calixresorcarenes, NMR 55 1070 calixresorcinarene 120 caranylboranes 935 C-alkylation, enolate anions 479 calorimetric measurements 355 carbamates 714 C-aromaticity 96 and acidity scales 354 addition to alkenes 931 C-calculation, phenoxide ions 480 calorimetric methods, and kinetics alkylation 588 C-nitroso compounds 634 300 and oxyamination 1020 Cadiot-Chodkeiwicz reaction 876 calorimetry 333 and the Knoevenagel reaction cage complexes, cyclodextrins Cambridge structural database, 1189 127 and hydrogen bonding 107 by carbonylation of amines, cage compounds 122 camphene 1351 with alcohols 765 cage structures, and urea 168 camphor 181 by electrolytic carbonylation of caged radical pair 1383 camphorsulfonate anion 394 amines 765 Cahn-Ingold-Prelog (CIP rules) Candida Antarctica lipase B 1220 by Hofmann rearrangement Cahn-Ingold-Prelog rules, and Cannizzaro reaction 1600 1370 absolute configuration and dihalides 484 conjugate addition to 149–152 and diions 1602 conjugated ketones 977 and alkenes 176 and hydride transfer 1441 cyclic, from isocyanates and and diastereomers 160 and the aldol reaction 1601 oxetanes 1105 and diastereotopic 186 crossed 1601 via Hofmann rearrangement and E/Z isomers 176 and the Tollens’ 1371 and enantiotopic 186 condensation 1601 enol 921 and groups 149–152 and the Tollens’ reaction carbamates, from alcohols 765 and the steering wheel model 1193 from alcohols with isocyanates 151–152 enantioselectivity 1601 1105 R/S nomenclature 149–152 in D2O 1602 from amines 501 calcium bisamides 703 intramolecular 1601 from carbonates 1241 calcium ions, and crown ethers mechanism 1601 from chloroformates and 120 reduction of aldehydes 1540 amines 1240 calcium peroxide diperoxohydrate, tetrahedral intermediate 1602 hydrolysis mechanism 1224 and singlet oxygen 869 canonical forms 6, 33, 46 See also lithiated allylic 1189 calcium, catalyst for Friedel-Crafts resonance reaction with isocyanates 1105 alkylation 649 acrolein 47 reduction to amines 1583 in amines, reduction of aromatic allylic carbanions 240 tert-butoxy, stability 1240 compounds 1526 allylic carbocations 441 torsional barrier 194 calculations, ab initio, and Lewis and 1,3-dipoles 1028 with aldehydes or ketones, base strength 358 and aromatic compounds 60 enantioselectivity 1189 and nitrenes 276 and heteroatom stabilized with Grignard reagents and nonclassical carbocations carbocations 230 588–589 427 and hyperconjugation 49, 94 with NBS and DBU 1371 norbornyl carbocation 436 and N-ylids 241 carbamic acids, by hydrolysis of calculations, acidity, ab initio 346 and vinyl chloride 42 isocyanates 1105 and conformations 188 aniline 48 carbamoyl amines 1238 and isotope effects 305 aromatic rings 59 carbanions 223, 895 and prismane 212 benzylic carbanions 240 carbanions, allylic 239, 694 azaannulenes 80 benzylic carbocations 228 [3+2]-cycloaddition, carbocation stability 231 cyclopentadienide ion 63 mechanism 1034 Mobius¨ aromaticity 88 dendralenes 45 carbanions, α-ammonium 693 nonalternant hydrocarbons 69 enolate anions 100 carbanions, and conjugation 239 SCF 37 ethylene 47 cyclopropyl stabilization 240 strain energy 207 +M and –M effects 376 field effects 241 wave mechanical 5 naphthalene 59 fused aromatic compounds 278 calicene, and aromaticity 68 nitro compounds 102 homoenolates 242 calix[4]azulene 120 of molecules 6 hybridization 242 calixarene-based rotaxanes 120 phenanthrene 60 isoracemization 692 calixarene–proton complex 120 pyrrole 63 organomagnesium compounds calixarenes 119, 583 triphenylmethyl radical 255 238 and atropisomers 144 capped cyclodextrins 127 organometallic compounds 237 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1955

pyramidal inversion 243 trifluoromethylsulfonyl and X-ray crystallography 272 racemization 242 stabilization 239 and ylids 727 rearrangement 250 triphenylmethyl 239 carbenes, bicarbenes 269 resonance 243 trivalent 237 Buchner¨ ring expansion 1070 resonance stabilization 243 via decarboxylation 249 by decomposition of retention of configuration 243 via deprotonation 249 diazomethane 1073 spectroscopic analysis 240 vinyl 243 chiral 269 substitution at vinyl carbon vinyl and configurational CIDNP 728 447 stability 244 coupling 273 carbanions, aromatic 242 with aldehydes 250 cyclopropane rearrangements as a base 237 with alkyl halides 249 273 benzylic 239 with electrophiles 249 decay, singlet to triplet 267 chiral 243 with ketones 250 decomposition of diazoalkanes conjugated to heteroatoms 240 carbazoles, preparation 515 270 d-orbital overlap 693 carbene–carbene rearrangement definition 266 definition 237 1364 diaryl 267–268 dinitromethane 240 carbenes 223, 266–275, 1068 diboron 268 diphenylmethyl 239 carbenes, acyl 274 dichloro 268 fate of 249 rearrangement to ketenes 273 dichlorocarbene 266 formation of a stable salt 240 carbenes, addition 1022 dichloromethylene 266, 269 carbanions, from alkenes 249 of imines 272 dimerization 272, 727 from cleavage of alkoxides 751 reactions 272 disproportionation 727 from radicals 309 to alkenes 267, 272, 1067 electrochemical generation 270 carbanions, generation of 249 to alkenes, rate constants 1069 electrophilicity 1068 halo, with aryl nitro compounds carbenes, alkylidene 269, 728 fate of 269 820 allylic insertion, rearrangement formation of cycloheptatrienes intermediates, and 725 1073 Wolff-Kishner reduction allylic, and rearrangement 726 formyl, lifetime 271 1578 amino 269 fragmentation 274 lifetime 240 carbenes, and amidation 873 carbenes, from alkyl halides 270 mechanism 939 and bond angles 268 from carboxylate ions 270 mechanism, and E1cB reactions and bond rotation 267 from cyclopropane dihalides 1281 and cleavage of diazoalkanes 1358 Na or K counterions 244 494 from cyclopropane photolysis nitrile 240 and [1+2]-cycloaddition 1067 270 oscillation 243 and diazo transfer reactions from diaziridines 271 overlap with d orbitals 241 1071 from diazirines 271 oxidation to radicals 250 and diazoalkanes 495 from diazoacetates 729 planar 691 and diazonium salts 725 from diazoesters 728 protonation of 237 and elimination 274 from diazomethane 267, 270 racemization 691 and EPR 268 from ketenes 270, 328 rubidium or cesium 244 and hemicarcerands 269 carbenes, generation by reaction with a proton 249 and Hund’s rule 267 ultrasound 726 resonance stabilized 239, 691 and insertion 725 generation of 269 solvation 242 and ionic liquids 1071 geometry 269 solvent effects 691 and IR 268 halo 1068–1069 carbanions, stability 237–238 and isomerization of heterocyclic 268 and hybridization 241 cyclopropanes 272 heterocyclic, and and hyperconjugation 241 and IUPAC mechanisms 467 cyclotrimerization 1078 and lone electron pairs 241 and leaving groups 468 hydrogen abstraction 727 and s character 238, 241 and metal catalysts 1073 in an argon matrix 268 order 239 and nitrogen extrusion reactions insertion reactions 272, 725, carbanions, stabilization 756 1330 1068, 1073 and the counterion 242 and nonbonded electrons 266 enantioselectivity 726 by nonadjacent π-bonds 242 and radicals 261, 727 homologation 725 by S or P 241, 243 and resolution 171 labeling 726 by sulfonyl 241 and ring expansion 1073 mechanism 726 carbanions, stabilizing groups and sonochemistry 333 isolation of 266 242, 752 and spin trapping 268 ligand, chiral imidazolinyl stable bridgehead 243 and stereochemistry 268 1143 strain and stability 241 and substitution 274 metal 726 structure and stability 242 and synthesis 272 metal catalysts 1070–1071, thioether, alkylation 578 and Wolff rearrangement 274 1426 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1956 SUBJECT INDEX

carbenes, generation by ultrasound carbenoids, and cyclopropanation and alcohol addition to alkenes (Continued) 1075 916 metal, cyclotrimerization, and cyclopropanation, and alcohol dehydration 495 formation of heterocycles enantioselective 1075 and alkene hydration 913 1079 and diazoalkanes 494–495 and alkyl halides 226, 412 methylene 266, 269 and dibromomethane 1074 and allylic rearrangement 441 migratory aptitude 728 and diiodomethane 1074–1075 and arenium ions 608 carbenes, N-heterocyclic see and organozinc compounds and azulenes 229 NHC 1074 and benzene 608 carbenes, N-heterocyclic 737 and ring expansion 1359 and bond angles 378 and tautomerism 101 and the Simmons-Smith and carbonylation of alkyl carbenes, octylidenes 269 procedure 1074 halides with alcohols 604 oxychloro 274 and ultrasound 1074 and chair conformations 234 photolysis 727 and zinc 1074 and chemical shifts 234–235 reaction with diazoalkanes 273 carbenoids, chiral 269 and conjugated dienes 228 reactivity 272, 726 definition 271 and conjugation 227 carbenes, rearrangements elimination reactions 271 and cyclopropyl groups 229 272–274, 1068, 1349 formation of 1074 and cyclopropylmethyl groups See also rearrangements homologation 725 436 ketones 1364 insertion, aminals 730 and Demyanov rearrangement carbenes, retro-Buchner¨ reaction insertion oxiranyllithium 1357 1070 reagents 730 and diazonium salts 467, 1351 silyl 269 intermediate 1074 and double hyperconjugation singlet 266 lithium chloride 730 227 decay to triplet state 267 mechanism of formation 1074, and E1 mechanism 1280 solid state 272 1309 and electrophilicity 410 solvent effects 271–272 preparation 1070 and ESCA 439 stability 266, 272 titanium, Tebbe reagents 1203 and formation of double bonds stable 272 zinc 1074 236 structural variations 1068, 1349 carboalkylation, intramolecular, of and Friedel-Crafts alkylation structure 266 dienes 948 653, 1336 to alkenes, activation energy carbocations 223, 410, 1089 and Friedel-Crafts reactions 1068 See also carbenium ions, 939 to carbene rearrangement 1364 oxocarbenium ions and Hofmann Martius reaction transfer 1068 carbocations, acetyl 230 680 transient grating spectroscopy carbocations, acyl 230 and homoconjugation 227 271 stability of 230 and hydration of alkenes 912 trapping in a matrix 266 carbocations, acylium ions 230 and hydride extraction 1441 trapping in an Ar matrix, adamantyl 233–234, 1340 and hydride shifts 1351 spectra 1365 addition of alkenes 236 and hydride shifts, energetics triplet 266, 1068 alkene neighboring groups 427 1351 persistent 267 alkenes, from dicarboxylic and hydrocarboxylation 984 vinyl 269 acids 1475 and hyperconjugation 94, carbenes, with alkenes, IR 1068 alkynyl, isotopic labeling 448 226–227, 233–234, 306, mechanism 1068 alkynyl, stability 448 452 rate constant 1069 carbocations, allylic 42, 228, carbocations, and insertion 725 steric hindrance 1070 694 and ion pairs 225 sterochemistry 1069 and cyclopropyl carbocations and IR 225, 233 structural features 1070 1357 and leakage 1343 carbenes, with alkynes 1072 and ion pairs 442 and leaving groups 1351 with aromatic compounds 271 and rearrangement 452 and NMR 225, 233–234, 429, with conjugated dienes 1070 and resonance 452 432 with heterocycles 1073 [3+2]-cycloaddition 1035 and nonclassical carbocations with imines 1167 from cyclopropanes 1397 436 with ketenes 1070 from cyclopropyl halides 456 and norbornyl bridgeheads 413 with thioketones 1208 from dienes 898 and norbornyl compounds 414 carbenium ions 224 See also HOMO 1397 and phenonium ions 431 carbocations resonance 441 and planarity 413 and halogenation of alkenes carbocations, and absolute and polyene cyclization 944 994 configuration 427 and Raman 233 carbenoids 1068 and adamantyl substrates 451 and rearrangement 724, 894, addition to alkenes 1067 and addition of alkyl halides to 913, 1336 alkene 730 alkenes 1004 and resonance 235, 452 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1957

and reverse Friedel-Crafts destabilizing groups 454 and NMR 427, 429, 435 alkylation 682 detection of 413 and norbornyl systems 426 and ring expansion 1356 deuterium labeling, and and nortricyclane 435 and SN1 mechanisms 1336 rearrangements 1339 and rearrangement 436 and SN1 reactions 410, 413, dications 229 and solvolysis 427–428 1351 direction of rearrangement and stability 435 and solvolysis 377 1336 and X-ray electron of alkyl halides 306 dissociation energy, table 232 spectroscopy 435 carbocations, and spectroscopic dodecahedral 234 arguments against 426, 434 analysis 233 equilibration of 439 controversy 1352 and strain 378 fate of 234 cyclopropylcarbinyl 426 and superacids 225, 410, 439, formation by ionization of alkyl π route 426 759, 1398 halides 235 σ route 426 and the Hammond postulate formation of a stable salt carbocations, norbornadienyl, and 450 240–241 NMR 427 and the Prins reaction 1213 and substituent effects 451 carbocations, norbornyl 907, 1352 and the tetrahedral mechanism and zeolites 235 ab initio calculations 436 1089–1090 Friedel-Crafts alkylation 651 and NMR 436 and UV 413 carbocations, from alcohols 226, classical argument 434 and Wagner-Meerwein 235 in stable solutions 435 rearrangements from alkanes 226, 526, 759, stability 435 1350–1351 1353 carbocations, on Zeolite Y 231 and Zaitsev’s rule 1351 from alkenes 235, 894 pentadienylium ion 225 carbocations, arenium ions 228, from alkyl diazonium PES 232 609 compounds 235 phenyl 230–231 aromatic 230 from amines 235 photochemical generation 413 aryl, and tritium decay 449 from anions and nitrous acid pK 231 benzoyl 230 235 planar 414 benzylic, canonical forms 228 from diazo compounds 1339 primary, and the SN1 bicyclic compounds, from radicals 265 mechanism 451 rearrangements 1342 carbocations, gegenion 225 propargyl 228 bicyclobutonium 438 generation of 234 propeller shaped 233 bridged 425 geometrical structure and rate of reaction with bridgehead 232–234, 414 migratory aptitudes 1342 nucleophiles 459 by reduction of radicals 749 heteroatom stabilized 230, 235 reaction with cyclopropanes calculations of stability 231 homoallylic 426 907 canonical forms 230 imidazolium 230 reaction with nitriles 1257 charge distribution 228 in–out isomerism 111 reaction with nucleophiles conjugation with cyclobutanes intermediates 225 235–236 229 isolable 454 rearrangements 225, 236, 759, conjugation with cyclopropanes long range rearrangements 917, 604, 939, 1351 229 1344 resonance stabilized 486 conjugation with heteroatoms loss of a proton 236 sequential 1,2-shifts 1344 230 mechanism 1309 silyl 235 counterion 225 memory effect 1343 carbocations, stability 229, 231, coupling with alkanes 724 methoxymethyl 230 233, 724 cubyl 234, 413 methyl, X-ray 224 in strong acids 225 and ab initio calculations 413 multiple, 1,2-shifts 1353 and cleavage of alkanes 759 cyclobutyl 1356 neopentyl 1351 and direction of rearrangement cyclobutyl and larger 229 rearrangement 1339 1337 cyclopropenium 230 neophyl 1351 and hydride shifts 1351 cyclopropenyl 72 NMR data, table 234 and Markovnikov’s rule 902 cyclopropyl, and ring opening nomenclature 224 and NMR 1337 1397 nonclassical 234 and solvolysis 414 cyclopropylcarbinyl 426, 1356 carbocations, nonclassical 425, and X-ray crystallography 224 [1,2]-sigmatropic hydrogen 1352 stabilization by alkyl groups shift 1357 ab initio calculations 427 894 and Demyanov and 1,3-Wagner-Meerwein by cyclopropyl groups 426 rearrangement 1357 rearrangement 1352 by oxygen 1213 cyclopropylmethyl 229 and cyclobutyl groups 436 carbocations, stabilizing groups, and NMR 438 and cyclopropylmethyl 436 and migratory aptitudes degenerate 1337 and delocalization 426 1341 delocalized, table 228 and laser Raman 435 and rearrangements 1341 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1958 SUBJECT INDEX

carbocations, stable solutions of and substitution reactions phenylboronic, and metal 225 474 catalyst 670 stereochemistry 234, 1352 as a guest 124 as a leaving group 1324, 1331 structure and delocalization as a leaving group 683, 1323, as ligand 116 227 1325, 1332 carbonylation of alkyl halides substituent effects 234 as a solvent 876, 1542 604 α-substitution 453 carbonylation of aryl halides of amines 764 superacids 1345 821 extrusion from cyclobutanone tert-butyl 226, 230, 724 critical temperature 392 1331 IR 224 electrofugal activity 684 extrusion from lactones 1325 carbocations, tert-pentyl, enzyme reductions 1542 hydrocarboxylation 982 rearrangement of 1337 formation of carbamates 765 preparation of divinyl ketones tervalent 698 from decarboxylation 683 604 thiacarbenium ions 235 isotope labeled 1161 reaction with Grignard reagents triarylmethyl 233 organometallic reagents and 551 trications 229 dienes 988 reaction with organolithium tricoordinated 232, 234 oxidation of alcohols 1448 reagents 551 trihomobarrelyl 234 supercritical, and alcohol source, benzene-1,3,5-triyl triphenylmethyl 228, 234 dehydration 392 triformate 670 trityl 228 and pyrrole, and Bacillus surrogates 821 tropylium 230 megaterium 668 thermal extrusion from ketones twisted 1343 and Stille coupling 718 1324 vinyl 231, 448 Suzuki-Miyaura coupling 800 with aryl halides and alcohols and p orbitals 448 synthesis 392 821 and tritium-decay 449 carbon dioxide, thermal extrusion with azides 764 stabilizing groups 448 from lactones 1324 with aziridines 1264 with alkenes 892 carbon dioxide, with amides 765 with boranes 1385–1387 with water 1213 with aryl halides and metal with diazonium salts 830 X-ray crystallography 224 catalyst 667 with epoxides 502 carbodiimides, by dehydration of with aryl halides with amines carbon NMR see NMR ureas 1328 786 carbon nucleophiles 544–545 from isocyanates and phosphine with aziridines 765 carbon radicals 223 oxides 1259 with epoxides 1106 carbon tetrachloride, and bond from thioureas 1260 flow reactions 1107 angle 27 from ureas 1328 with Grignard reagents 1160 and dipole moment 20 polymer-supported 1242 with organoboronates 1161 carbon tetrahalides see halides water soluble 1231 metal catalyzed 1161 as acceptor 116 carbohydrates, and cyclodextrins with organolithium reagent 743 Carbon-13 NMR Spectra 1622 126 with organometallics 743 carbon-14 772, 1339 and sonochemistry 333 with ylids 1201 and cyclopentadienide ion 63 cleavage, NHC catalyzed 981 carbon disulfide, and DCC 1127 as a radiolabel 296 carbolong complexes 89 with alcohols 1106–1107 labeling 295 carbomagnesiation of alkenes 946 and NaOH 1304 carbon–H, hydrogen bonding of alkynes 946 with amines or anilines 1127 110 conjugated dienes 947 with hydroxylamine 1562 carbon–metal bonds 237 intramolecular 947 with organometallics 1161 carbonates, allylic, and Pd carbon, mass spectrum of 225 carbon leaving groups 751 catalyzed coupling 566 carbon acids 346 carbon migrations, and the Tsuji-Trost reaction carbon dioxide, addition of [1,j]-sigmatropic 1405 564 amines 1127 carbon monoxide, amines with coupling 568 and arylboronic esters, and alkynes 988 palladium catalyzed reaction metal catalyst 668 and alcohols 604 with amines 515 and aryl iodides 664 and arylboronic esters, and carbonates, and resonance 42 and carbonylation 392 metal catalyst 668 conversion to chiral and catalysis 392 and aryl iodides 664 tetrahydroisoquinolines and Glaser reaction 876 and coupling reactions 547 529 and indole, and metal catalyst and hydrocarboxylation 984 cyclic 1107 668 and hydroformylation of dialkyl, from alkyl halides 501 and nucleophilicity 474 alkenes 989 ester salts 1107 and polymers 392 and the Koch reaction 982 from epoxides and carbon and reactivity 392 aryl halides, aryl iodonium dioxide 1106 and SN1andSN2 reactions 470 compounds, and metal flow reactions 1107 and sodium phenoxides 668 catalyst 670 from haloformic acids 1106 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1959

from phosgene and alcohols of amides 605 carboxylates, ammonium, from 1106 of aryl halides, with carboxylic acids and methyl magnesium, with organometallics 822 ammonia 1241 ketones 1192 of azides 764 pyrolysis 1241 photochemistry 1193 of boronic acids 605 carboxylates, lead, chiral, and methylmagnesium, indirect of imines 988 cleavage of diols 1464 carboxylation 1192 of organometallics 603, 605, radioactive 295 propargyl, rearrangement to 743 reaction with thiols 508 allenes 1320 of phenols 669 carboxylation, alkenes with carbon propargylic 507 carbonylation, Reppe 982 dioxide 987 unsymmetrical 1107 carbonylative Stille coupling indirect 1192 with amines 1241 719 metal catalyzed 606 carbonium ions see carbocations cross coupling 561 of alkenes, metal catalyzed carbonyl carbon, and HSAB 463 triarylbismuths 803 988 and nucleophilicity 463 carbonylimidazole 1244 organometallics, flow reactions nucleophilicity order 463 carbonyls, addition of alcohols 743 carbonyl compounds, acyl 1101 reductive, of alkenes 982 addition 1087 addition of water 1095 metal catalysts 983 conjugated, addition of and bonding 12 carboxylcoumarins, by solvent organometallics 960 and Cram’s rule 1088 free aldol reaction 395 cyanation 723 approach of nucleophiles carboxylic acid salts, with acyl α-hydroxylation, reagents 1483 1092 halides, formation of pKa, α-proton 579 catalysis of nucleophilic attack, anhydrides 1235 carbonyl coupling, and low valent by nucleophiles 1092 carboxylic acid salts, with SOCl2 titanium 1597 complex with hydrides 1536 1236 carbonyl nitrenes 715 conjugated and reactivity 1088 carboxylic acids, acidity 21, insertion 715 conjugated with alkyl halides 355 carbonyl oxides, 1151 alcohols see hydroxy acids [3+2]-cycloaddition 1030 directionality of approach of alkyl halides with NaNO2 604 and ozonolysis 1468 nucleophiles 1092 alkylation 586 carbonyl ylids, facial selectivity 1088 with diazo compounds 502 [3+2]-cycloaddition 1030 formation of stereoisomers allylic, decarboxylation 754 carbonyl-ene reaction 954 1088 carboxylic acids, and alkylation of carbonylation, akenes, metal fragmentation of halo ethers pyridine 880 catalyzed 984 1321 and field effects 21 and the Baylis-Hillman reaction from methylene 1477 and free energy 372 985 halo, with boronic acids 820 and hydrogen bonding 106 and the Pauson-Khand reaction nucleophilic addition 1088 and inductive effects 21 985 pKa of α-proton 579 and ionization 372 alkenes 984 seleno 716 and resonance effects of pKa carbonylation, alkyl halides, metal sulfenyl 716 363 mediated 603 trajectory of nucleophilic and tautomerism 103 alkynes 984 approach 1092 and the Koch-Haaf reaction and formation of amides 669 with hydrogen sulfide 1107 982 and supercritical carbon dioxide with Lawesson’s reagent 1109 and the Schmidt reaction 1373 392 carbonyls, conjugated see and the Wolff rearrangement aryl halides with alcohols 821 conjugated carbonyls 1364 aryl halides, microwave carbophilic addition 1087 carboxylic acids, aromatic, and the irradiation 821 carborane acids 351 Hammett equation 381 dienes 984 carboxylate anions, and lactone carboxylic acids, aryl conversion double 605 formation 500 to diketones 1599 formation of amides 764, 1249 and organolithium reagents and iodonium salts 667 formation of ureas 764 1154 and labeling 668 intramolecular, with aryl and the Kolbe reaction 885 and phosgene 667 halides 821 aryl, rearrangements 684 and the von Richter metal catalysts, enantioselective conversion to isocyanates 1260 rearrangement 834 982 decarboxylation 752 by oxidation of aromatic side mechanism 983 formation of carbenes 270 chains 1472 metal catalyzed 605, 982 radical coupling 885 CCl4, Reimer-Tiemann reaction carbonylation, of acyl halides 670 rearrangement, and Henkel 668 of alcohols 604 reactions 684 from aryl nitro compounds of alkyl halides 605 resonance 684 834 metal catalyzed 604 with cyanogen bromide 1260 Kolbe-Schmitt reaction 668 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1960 SUBJECT INDEX

carboxylic acids, as nucleophiles dilithiated 734 with borane 1547 1218 enol content 98 metal catalysts 1547 benzoic see benzoic acid esterification and azeotropic with enzymes 1547 bromo 147 distillation 1229 with hydride reagents, carboxylic acids, by cleavage of and steric hindrance 378 selectivity 1547 ketone esters 757 exchange with acyl halides with silanes 1551 by hydrolysis of anhydrides 1251 with silanes and UV 1551 1218 with amides 1236 carboxylic acids, reversible of carboxylic esters 1219 with esters 1236 esterification 1229 of ketenes 1364 field effects and pKa 363 structural limitation of of nitriles 1099 formation of hydrazones 710 decarboxylation 753 of alcohols 866 carboxylic acids, from acyl structure and decarboxylation by oxidation of alcohols 1492 halides 1363 753 of alcohols, and microwaves from alkyl halides 604, 951 table of ionization 373 1492 from alkynes 988 thermodynamic values, table and oxammonium salts 1492 from anhydrides and alcohols 373 and TEMPO 1492 1227 via the haloform reaction 758 reagents for 1492–1493 from diazoketones 1363 vinyl, with NBS 887 of aldehydes 1494–1495 from diketones 757 carboxylic acids, with alcohols of aldehydes, reagents from esters 1219 1229 1495–1496 from cleavage of diketones 757 acid catalyzed 1228 of enol ethers 1500 from Grignard reagents and catalysts 1229 carboxylic acids, by oxidative CO2 1160 cyclization 1230 cleavage of alkenes 1470 from ketenes 1364 dehydrating agents 1231 by the Arndt-Eistert synthesis from ketones 710, 758, 1604 equilibrium 1228 1363 from malonic esters synthesis ionic liquids 1229 by the Barbier-Wieland 577 lactones 1230 procedure 1471 from nitriles 600 mechanism 1231 by the Willgerodt reaction 1604 from oxazolines 592 metal catalyzed 1229 by-products of epoxidation from peroxyacids, and alkenes Mitsunobu reaction 1230 1011 1011 solid state 1229 carboxylic acids, chain extension from primary alcohols with water soluble carbodiimide 1363 Jones reagent 1448 1231 cleavage of methyl ketones 758 carboxylic acids, halo 543 XtalFluor-E 1230 carboxylic acids, conjugated by lactone formation 286 carboxylic acids, with alkenes Perkin reaction 1190 with aldehydes or ketones 920 by the Doebner modification 1190 with alkenes, metal catalyzed 1188 carboxylic acids, halogenation 920 decarboxylation 752 708–709 with ammonia 1242 formation of vinyl nitro and radicals 709 with boranes 1522 compounds 874 electrolysis 709 boronic acids, metal catalyzed from alkynes 984 carboxylic acids, 1154 with nitric acids and AIBN 874 Hell-Volhard-Zelenskii with Burgess reagent 1242 carboxylic acids, conversion to reaction 708 with chiral amines 584 aldehydes 1474 hydrolysis of acyl halides 1218 with cyanuric fluoride 1251 to alkyl halides, metal catalyzed of amides 1224 with DCC and H2O2 503 1238 Japp-Klingemann reaction 710 with diazonium salts, and CO to allenes 886 ketenes, reagents 1304 830 to amides 1241–1242 oxidative cleavage of alkynes with enol esters 1236 Lawesson’s reagent 1243 1471 with halogenating reagents metal catalysts 1242 oxidative decarboxylation to 1250 reagents 1243 alkenes 1474 with hydrazoic acid 1373 to hydroperoxides 503 mechanism 1474 with imidazole 1243–1244 to ketones, and radicals 1257 carboxylic acids, oxo 102 with isocyanides and carbonyls to nitriles 601 pKa, table 363 1265 to peroxy acids, reagents 1498 pyrolysis 1304 with Lawesson’s reagent 1237 to Weinreb amides 1243 reagents for conversion to alkyl with organolithium reagents carboxylic acids, decarboxylation halides 886 1153 751 carboxylic acids, reduction of with trichloroisocyanuric acid dehydration 1235, 1304 hydrocarbons 1583 1242 derivatives, aldol-like reactions to alcohols 1546 with triphenylphosphine and 1183 to aldehydes, reagents carbon tetrachloride 1250 dianions 588 1550–1551 carboxylic esters see esters JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1961

carboxylic esters, addition to from diazomethane and acids CAS Registry Number 1633 alkenes 980 502 CAS, databases 1633 allyl, with keto acids, metal from ethers 502 CASSI 1639 catalyzed 887 from halo ketones 1361 catalysis, acid or base, and ester carboxylic esters, and Claisen from hydrocarbons 870 hydrolysis 1219 condensation 1183, 1253 from ketones and peroxy acids catalysis, acid–base 355 and DBU 501 1378 catalysis, acid, epoxide and dimethyl carbonate 501 from methyl ketones 758 alcoholysis 496 and DMF acetals 501 from oxonium salts 501 of acetals 486 and Friedel-Crafts alkylation from trihalides 484 of epoxides 489 650 carboxylic esters, heteroaryl, by alcohols and diazo compounds and Katritzky carbonylation 821 494 pyrylium-pyridinium heteroaryl, from aryl halides and Brønsted catalysis equation method 501 821 355 and low-pressure hydrogenation hydride reagents 1548 and free energy 295 1548 hydrogenation 1548 and mechanism 295 and Schotten-Baumann hydrolysis 1219 and supercritical carbon dioxide procedure 1227 and mechanism 384 392 and SN2 reactions 469 metal catalyzed 1548 asymmetric, chiral poisoning and the Pinner synthesis 1106 carboxylic esters, reduction to 1515 and the Reformatsky reaction alcohols, Bouveault-Blanc base 356 1153 procedure 1548 base, and the Marcus equation and transesterification 1232 to alcohols, microwaves 1548 356 carboxylic esters, aryl, by reagents 1547 general 355 carbonylation 821 to aldehydes, reagents general acid 355, 487 base catalyzed condensation 1550–1551 Lewis acid, sulfonyl halides 1253 to ethers, reagents 1579 with halo esters 559 basic hydrolysis, isotope to methyl compounds 1583 metal, amination 516 labeling 1091 with Dibal 1551 organometallics coupling tetrahedral mechanism 1091 with silanes 1549 558–563 by Favorskii rearrangement with sodium in ethanol 1537 nucleophilic, hydrolysis of 1361 Bouveault-Blanc procedure anhydrides 1218 by hydration of alkynes 916 1537 catalysis, phase transfer see phase by hydrolysis of imino esters carboxylic esters, reductive transfer 1106 coupling to acyloins 1598 catalysis, specific 355 by oxidation of aldehydes 1495 solvent effects in alkylation specific acid 355 reagents for 1497 reactions 499 catalyst free, Friedel-Crafts by the Tischenko reaction 1602 sulfenylation 716 alkylation 652 condensation with aldehydes or thioethers 1018 thiols with vinyl ethers 922 ketones 1183 via Mitsunobu reaction 500 catalyst, abrine catalysts 310 condensation with ketones with amines or ammonia 1245 acid 1178 1255 with dimethyl sulfate 501 acid, polymeric 1230 conjugated, and the with Petasis reagent 1202 acid–base 355 Baylis-Hillman reactions with trimethylphosphate 501 alcohols, with carboxylic acids 1149 carbynes 269 1229 enol content 98 carcerands 125 anti-Markovnikov, hydration of exchange with carboxylic acids and cyclopentadiene 73 alkynes 915 1236 carciplex 125 antibody, [3+2] cycloaddition carboxylic esters, from acyl Caro’s acid, oxidation of amines to 1035 halides and alcohols 1488 hydroxylamines 1502 antibody, Diels-Alder reaction from acyl peroxides 870 oxidation of amines to amine 1037 from acyl tosylates 502 oxides 1504 aqueous Diels-Alder reaction from aldehydes, reagents 1602 oxidation of anilines to nitroso 1037 from alkyl halides 499 compounds 1502 asymmetric 310, 312 from anhydrides 502 mechanism 1502 and synthesis 165 and alcohols 1227 and thioamides 1111 azaferrocene 1364 from carboxylate salts 499 Carroll rearrangement, Claisen biocatalysts 310, 1210 from carboxylic acids and rearrangement 1417 bis(oxazoline) copper 962 alcohols 1228 carvone 1062 boric acid 1249 from carboxylic esters and carvonecamphor 1062 boronic acids 1242 alcohols 1232 CAS Online, replaced by Brønsted acid, from diazo compounds and SciFinder 1613 [3+2]-cycloaddition 1032 acids 502 CAS Registry 1617, 1633 Brønsted-Lowry acids 308 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1962 SUBJECT INDEX

catalyst, abrine catalysts catalyst, Friedel-Crafts 641 alkyne anions, with aldehydes (Continued) addition alkyl halides to alkenes and ketones 1144 Brønsted-Lowry acid, 1003 alkynes, hydrogenation 1516 Diels-Alder reaction 1037 alkylation 648 oxidation to diketones, metal catanionic, Diels-Alder reaction catalyst, from dihydroxylation of catalysts 1501 1038 alkenes 1006 tetramerization 1076 chemoentrapment 309 green see green catalysts trimerization 1076 catalyst, chiral see catalyst, heterobimetallic 1516 amide alkylation 529 asymmetric catalyst, heterogeneous 308 amination 636 chiral 367, 976, 1153, 1380 asymmetric 311 amines with aldehydes or and hydrogenation 165 and hydrogenation 1513 ketones 1112 Brønsted acids 508 catalyst, homogeneous 308, with esters 1246 Michael reaction 960 1513 and alkyne coupling 878 phosphine 1054 hydrogenation, Optically active catalyst, metal, and Barbier thiourea 1125 1529 reaction 1130 zinc 1178 mechanism 1518 and biaryls 795 catalyst, chromium 309 and hydrogenation 1513 and elimination of halo ethers to catalyst, Cinchona alkaloids 976, types 1514 alkenes 1320 1186 catalyst, hydrogen ion, and the and enols, preformed 1176 halogenation of ketones 707 tetrahedral mechanism and epoxide alcoholysis 497 Cinchona-derived, 1090 and Grignard reaction 1130 phase-transfer 1013 catalyst, hydrogenation, soluble and Hiyama coupling 546 Claisen rearrangement 1416 1513 and hydroformylation 989 clay 525 hypervalent iodine 311 and hydrosilation of conjugated cobalt, and cross coupling 561 imidazolidinones 1528 alkenes 1528 computer development 310 imidazolium 1054 and Meinwald rearrangement copper 309 imidodiphosphate, confined 1355 and cyanation 795 954 and Michael reactions 957 Gomberg-Bachmann-Hey imidodiphosphoric acid 656 and Mukaiyama aldol reaction reaction 832 iodine 649, 978 1182 chromium–salen complex 1017 iodoimidazolium 569 and nitrenes 1024 Davies catalyst 308 ionic liquid, hydroamidation, of and selenides 510 DBU, and aza-Michael reaction alkynes 931 and the Boord reaction 1321 976 ionic, Diels-Alder reaction and the Heck reaction 811 definition 295 1037 and the Michael reaction 955 dendrimers 1264 iron 309 and the Pauson-Khand reaction development 308–312 and cross coupling 561 987 Diels-Alder reaction 1037 catalyst, Lewis acids 648, 1180, and the Ritter reactions 1258 dipalladium 988 1214 catalyst, metal, and dipeptides 1013 Heteroatom Diels-Alder α-hydroxylation of ketones dipeptides, for epoxidation reaction 1052 1483 1013 reactions 1215 aromatization 1443 dirhodium 308 catalyst, Lewis bases 1181 aryl ether formation 782 and carbene insertion 726 lipase, and aza-Michael arylation of silanes 822 DNA, and hydrolysis of amides reaction 976 asymmetric hydrogen transfer 1226 magnetically recoverable 800 1544 Doyle catalyst 308 magnetite impregnated with Baeyer-Villiger rearrangement Eosin Y 512 iridium 569 1378 thioether formation 783 manganese 311 boranes with aldehydes 1146 ferrous chloride and SRN1 449 catalyst, metal see metal catalysts boronates, with imines 1165 catalyst, for acylation of amines catalyst, metal 559 boronic acids, alkene coupling 1240 acyl halides with alkynes 1156 803 for alcoholysis of anhydrides with alcohols 1227 with aldehydes 1146 1228 alcohols, allylic, oxidation with imines 1165 for alkene metathesis 1427, 1449 with nitrile 1169 1430 with anhydrides 1228 boronic esters with aldehydes for Dieckmann condensation with carboxylic acids 1229 1147 1255 aldehydes, with alkenes 981 carbenes 1070–1071 for Friedel-Crafts alkylation alkene metathesis 1426 carbonylation 982 649 alkoxysilanes with aldehydes carboxylic acids, conversion to for hydrogenation 1513 1105 amides 1242 for Tischenko reaction 1602 alkyl halides, from carboxylic with borane 1547 for transesterification 1233 acids 1238 carboxylic esters 1548 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1963

catalytic hydrogenation, lactones, from epoxides 1359 catalyst, palladium 44, 308, 311 aldehydes and ketones Mannich reactions 1125 and Suzuki-Miyaura coupling 1536 Michael addition 960 799 Claisen rearrangement 1416 Mukaiyama aldol reactions and the Heck reaction 811 conversion of aziridines to 1181 arylation of amines 787 amines 1318 Nazarov cyclization 958 arylation of ketones 819 Cope rearrangement 1410 Oppenauer oxidation 1450 polymer supported 787 coupling with silanes 545 catalyst, metal, oxidation silylation of 822 catalyst, metal, 1477–1478 Sonogashira coupling 816 [2+2]-cycloaddition 1057, of alkenes to aldehydes or Stephens–Castro coupling 816 1059 ketones 1499 thiocarbamate formation 765 forbidden 1396 catalyst, metal, oxidative trifluoroborates with aldehydes [2+2+2]-cycloaddition 1081 decarboxylation 1474 1147 [3+2]-cycloaddition 1032 oximes, dehydration to nitrile catalyst, phase-transfer 257, 956 catalyst, metal, cyclotrimerization, 1325 catalyst, phosphazenes 310 triynes 1078 pinacol coupling 1594 phosphines 1261 decarboxylative addition 887 radical cyclization 974 and the Michael reaction 956 coupling alkynyl acids 888 catalyst, metal, rearrangement of polymer-supported 801, 811, dehalogenation of acyl halides vinyl epoxides 1355 977 to ketenes 1320 cyclopropylcarbinyl 1357 polystyrene resins 477 of dihalides 1319 formation of allenes 1319 proline esters 310 dehydrohalogenation 1312 catalyst, metal, reduction of proteins 1150 diamination 1021 conjugated alkenes 1527 pybox, and amination 516 diazoacetates with alkenes reductive amination 1119–1120 radical cation, Diels-Alder 1022 metal–salen complexes 1017 reaction 1038 enamines, from amines 1446 silanes, reduction of aldehydes recoverable 811 enol ether reactions 5819 or ketones 1541 recyclable, and alkene enolate anion 583, 1175 sulfides oxidation to sulfones metathesis 1429 epoxidation 1011 1506–1508 relay 311 epoxides and amines 523 thio-Michael addition 978 reusable, Friedel-Crafts esterification of aldehydes with thiols with aryl halides 783 acylation 662 alcohols 1497 transamidation 1237 rhenium 309 for dehydrogenation of alcohols transfer hydrogenation 1520 rhodium 308, 764 1454 vinylcyclopropane catalyst, ruthenium scavenger for epoxidation 1012 rearrangement 1407–1408 resins 1429 for hydroboration 936 Wacker process 1499 ruthenium–salen complex 1017 for the ene reaction 952 with acyl halides 1315 Schiff base 995 for transesterification 1233 with esters and base 1254 selenophosphoramide 1025 Grignard coupling 881 with Grignard reagents 553 Shibasaki 311 Grignard reagents, ultrasound catalyst, manganese–salen Shvo’s catalyst 914 1163 complex 1017 silica-supported 811 with imines 1163 molecular catalysts 310 silver 309 Heck reaction 814–815 catalyst, N-heterocyclic carbenes silver, alkylborane coupling Henry reaction 1186 see catalyst, NHC 883 heteroatom Diels-Alder catalyst, NHC 949, 1150, 1249, sludge 1353 reaction 1053 1496, 1498 sulfuric acid 1103 hydride reagents, reduction of and vinyl boronates 936 taurine and homotaurine 1506 nitriles 1556 Grignard reaction 1131 TEMPO, and aza-Michael catalyst, metal, hydrogenation hydrocyanation 1211 reaction 976 1513, 1515 Staudinger reaction 1058 tetrabutylammonium chloride, of amides 1583 catalyst, nickel 308–309 Grignard reaction 1132 of imines 1554 and amination 518 thiazolium salts, benzoin catalytic, cyclopropanes 1530 and cross coupling 561 condensation 1216 heteroaryl halides 1570 and Ullmann reaction 798 titanium 309 reduction of nitriles 1556 catalyst, optically active 135 titanium compounds 1017 catalyst, metal, imines, from catalyst, organocatalysts titanium–salen complex 1017 amines 1461 309–310, 1210 titanocene/zinc 311 with diazo compounds 1167 catalyst, osmium 309 TPAP oxidation 1454 catalyst, metal, isomerization of magnetically recoverable transition metals, alkylation of allylic alcohols 1367 1008 amides 528 ketones, from epoxides, metal catalyst, oxazaborolidines 310 triphase 477 catalysts 1355 oxocarbenium ions 310 urea, and nitrene insertion 715 Knoevenagel reaction 1187 catalyst, palladacycles 813, 986 ureates 311 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1964 SUBJECT INDEX

catalyst, ruthenium scavenger cations, aryl 829, 832 Chemical Abstracts 1613, 1633 resins (Continued) bicyclic 111 Service Source Index (CASSI) uronium salt 1244 radical 850 1639 Wilkinson’s 43–44 separation with crown ethers and SciFinder 1614 hydrogenation, mechanism 118 collective indexes 1616 1518 vinylic 895 table 1617 ytterbium, amines with cavitands 119, 332 index guide 1616 oxetanes 525 cavitation, acoustic, and cavitation organization 1614 Ziegler 942 noise 332 Registry number 1617 catalytic dehydrogenation, of and sonochemistry 331 SciFinder 1607 alcohols 1454 and ultrasound 477 chemical induced dynamic catalytic Hunsdiecker reaction noise, and acoustic cavitation electron polarization see 886 332 CIDEP catalytic hydrogenation see CD see circular dichroism chemical properties, and Beilstein hydrogenation cell length, and specific rotation 1618 catalytic Wagner-Meerwein 135 chemical shift 19 rearrangements 1353 cellosolve 497 alkenes 55 catalyzed, acid see acid catalyzed center of symmetry, and chirality and annulenes 84, 86 catecholborane, and conjugate 136 and antiaromaticity 74 addition 969 ceric ammonium nitrate, and and benzenonium ion 611 with alkenes 969 acetal cleavage 488 and cyclobutadiene 74 catenanes 114, 127, 130 and nitration of aromatic and electronegativity 19 acyloin condensation 1598 compounds 631 and hydrogen bonding 109 and chirality 147 cesium fluoride, base 514 and paramagnetic ring current and daisy chains 128 cesium hydroxide, base 514 56 and mass spectrometry 130 cesium, alkyls 244 and ring current 55 and molecular necklaces 128 cesium, aryls 244 annulenes 87 and π–π interactions 129 α-CH oxidation, of methyl homoaromatic compounds 90 cyclic 128 aromatic compounds 1478 and carbocations 234–235 diastereomers 130 and the Etard´ reaction 1479 and conformations 188 doubly interlocking 130 CH—π interactions, aryl 113 chemically induced dynamic enantiomer separation by chain elongation, and boranes 967 nuclear polarization see HPLC 130 and alkene metathesis 1426 CIDNP heteroatom 129 chain reactions 843 Chemisches Zentralblatt 1617, interlocked 129 and SET mechanism 420 1639 liquid crystals 128 chain termination, and Free radical and literature searches 1632 rotation of units 129 addition 897 chemoentrapment, catalyst 309 synthesis of 128 chair conformation 195 chemoenzymatic dynamic kinetic topological stereoisomers 129 chair transition state, Claisen resolution 172 cathecols and hydroquinones, rearrangement 1415 chemoselective reducing agents, oxidation with Fremy’s chair-to-chair interconversion 195 for aldehydes rather than salt 1459 channel-type complexes 127 ketones 1533 oxidation with Oxone 1459 Chapman rearrangement 1435 for ketones rather than with periodate 1459 mechanism 1435 aldehydes 1533 mechanism 1460 charge densities, arenium ions chemoselectivity, definition 1533 reagents 1459 619 Diels-Alder reaction 1037 cation affinity 459 charge distribution, in conjugated hydride reagents 1533 cation–molecule pair 418 carbocations 228 oxidation, of alcohols, with and SN2 reactions 418 charge separation, and Bobbitt’s reagent 1453 cation–π interactions 113 hyperconjugation 95 reduction of alkyl halides 1568 cationic catalysts, Diels-Alder and resonance 47 Chemtracts: Organic Chemistry reaction 1038 charge transfer, bonding 117, 119 1625 cationotropic rearrangements complexes 114 Chichibabin reaction 823 1335 UV, and solvents 473 and NMR 823 cations, allylic 1358 spectra 114 mechanism 823 and the cyclic mechanism 898 Charton’s ν values 388 structural limitations 823 resonance 898 chelated transition state 1176 chiral absorbents 169 thermodynamic stability 898 chelation, and dialkylamide bases chiral additives, amines 1177 1,2 versus 1,4 addition 898 369 and dihydroxylation of alkenes cations, alternant hydrocarbons cheletropic reactions, cyclic 1008 69 sulfones 1317 and resolution 170 and phase transfer catalysis 477 mechanism 1317 and the Claisen condensation annulenium 90 ChemDraw 1651 1184 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1965

boranes, in reductions 1544 and prochiral 184 catalytic hydrogenation 1515 Cinchona alkaloids 960 and racemates 135 in catalytic hydrogenation cyclopropanation 1072 and restricted rotation 145 1515 in hydride reagents 1544 and specific rotation 155 chiral Lossen rearrangement sparteine 960 and symmetry 134, 136 1372 with hydride reagents 1544 and synthesis 161–166 metal catalysts 1053 chiral allenes 557, 700 and the Cornforth model 163 molecules 133–134 chiral amide bases 370 and the Felkin-Anh model 163 and stereogenic atoms 138 chiral amines 140 chiral, compounds, atropisomers from achiral precursors 163 chiral additive 1177 142 N-heterocyclic carbenes 949 chiral ammonium salts 1212 Cahn-Ingold-Prelog system palladium complex 1379 chiral atoms see stereogenic 149–152 phase transfer agents 576 chiral atoms, and optical activity chemical reactions 152 phosphine-catalyst 1054 138 chiral pool 161 poisoning, in asymmetric and symmetry 138 cyclooctatetraene 146 catalysis 1515 definition 137 cyclooctene 146 pool, and synthesis 161 chiral auxiliaries, aldol cyclophanes 145 reactions see enantioselectivity condensation 1178 D/L nomenclature 149 reagents, for reduction of and asymmetric synthesis 164 diastereomers 158 ketones 1542 and Baylis-Hillman reaction epimers 159 recognition, and diastereomers 1151 erythro/threo nomenclature 160 169 and Diels-Alder reactions 1040 from achiral compounds 163 and resolution 169 and Reformatsky reaction 1153 fulgide 145 rotaxanes 130 definition 164 glyceraldehyde 148 Schiff base 1140, 1508 imines, with organolithium helical 144 selenium ylids 1205 reagents 1162 helicene 144 solvating agents, for NMR 175 Mannich reactions 1124 heptalene 145 solvents, and NMR 174 chiral, axis see axis, chiral Lewis acids 367 sulfoxides 1419 chiral, aziridines 532 meso form 158 sulfur ylids 1205 binapthols 168 metallocenes 145 zinc catalyst 1178 bis(hydroxyamides) 1017 nitroxide radicals 259 chirality see chiral compounds, boranes 935 optical purity 173 enantiomers Brønsted acids 1554 pseudoasymmetric carbon 159 chirality, adamantanes 140 carbanions 243 rate of reaction 134 chirality, and 2n rule 159 carbenes 269 resolution 140 and a Mobius¨ strip compound catalysts 976, 1380 spiranes 144 147 and dihydroxylation of stereoselective synthesis 162 and absolute configuration 148 alkenes 1008 syn/anti nomenclature 161 and allenes 141, 144 and Reformatsky reaction torsional diastereomers 143 and alylidenecyclohexanes 1153 with multiple stereogenic atoms 145 Michael reaction 960 158 and asymmetric induction 165 chiral compounds see chirality, chiral, crown ethers 118, 169 and axis of symmetry 136 diastereomers, enantiomers diazaboron derivatives 1184 and barrelene 146 chiral, compounds, adamantanes dioxiranes 1014 and bond rotation 244 140 discrimination 144 and bridgehead atoms 139 and 2n rule 159 hydrazines 1555 and calixarenes 147 and allenes 144 hydrogen transfer 1543 and carbanions 244 and axis of symmetry 136 imidazolinyl carbene ligand and catenanes 147 and biaryls 141 1143 and center of symmetry 136 and biphenyls 141 iminium salts 1015 and circularly polarized light and Cram’s rule 162 ionic liquids 394, 965 157 and diastereotopic 185 lanthanide shift reagents 174 and crown ethers 147 and diastereotopic faces 185 lead carboxylates, and cleavage and cumulenes 145 and enantiomeric excess 173 of diols 1464 and diastereomers 158 and enantiotopic faces 185 Lewis acidity 367 and enantiomers 134 and Fischer projections 148 chiral, ligands 565 and enantioselective reactions and GC 175 aldol condensation 1178–1179 165 and HPLC 175 and alkyl coupling 818 and epimers 159 and kinetic resolution 169 and dihydroxylation and handedness 134 and molar rotation 155 1008–1009 and helical shapes 144 and NMR 173 and reduction 1544 and heptahelicene 145 and paracyclophanes 145 and Sharpless asymmetric and hydrocarbons 147 and polarizability 138 dihydroxylation 1008 and isotopes 146 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1966 SUBJECT INDEX

chirality, and meso compounds oxidation of alkanes 1477 chloronium ions see halonium 158 with alkenes 1019 chlorophenylcarbene 271 and metallocenes 145 with pyridinium bromide chlorophosphates, chloro 1117 and mirror plane 136 perbromide 1003 chlorosulfenation 872 and molar rotation 154 and alkene halogenation 997 chlorosulfuric acid, with aromatic and molecular knots 147 chloramines, from amines 763 compounds 641 and optical activity 133 chlorides from tosylates 536 2-chlorothio esters, from and paracyclophanes 145 chlorides, acyl see halides, acyl episulfides 542 and pentahelicene 145 chlorides, acyl, by halogenation chlorothioformates, with amines and phosphates 138 862 1269 and phosphorus 183 acyl, from aldehydes 862 chlorothionoformates, conversion and plane of symmetry alkyl see halides to isothiocyanates 1328 136–137 and Grignard reagents 247 chlorotriethoxysilane, with and plane polarized light 157 from iodides 535 oxetanes 542 and polarizability 138 ammonium, with Grignard chlorotrimethylsilane, and the and pyramidal inversions 138 reactions 1129 acyloin condensation and quadrivalent stereogenic vinyl see vinyl chloride 1598 atoms 138 chlorination 858 with enolate anions 721 and resolution 135 allylic 863, 865 with propynyllithium 552 and restricted rotation 145 and NCS 863 chlorotriphenylmethane, and rotaxanes 147 aromatic compounds 642 ionization 228 and specific rotation 154 of alcohols 441 chlorotris(triphenylphosphine) and spiranes 144 of alkanes, selectivity 859 rhodium Wilkinson’s and substituted cyclohexanes of alkenes, reagents 994 catalyst 1513 198 of hydrocarbons, and cholest-6-en-3-one 380 and sulfones 138 mechanochemistry 338 cholesterol, biosynthesis 944 and superimposability 133, 138 of malic acid 405 cholic acid, and resolution 169 and symmetry 146 of methane 293 as host 124 and tervalent stereogenic atoms photochemical 850 choranil, and aromatization 1443 138 SNi′ reaction 443 chorine radicals 841 and trans-cyclooctene 145 chlorine cation 993 chromans, by Diels-Alder reaction and triarylamines 146 chlorine radicals 848 1054 and twisting 145 chlorobenzene, resonance 46 chromates, structural variation for chirality, asymmetric reduction chloroborane, mono see oxidation of alcohols 1448 164 monochloroborane chromatography, and resolution biaryls 802 chlorocarbene 1073 168 Cahn-Ingold-Prelog system chlorocarbenium ions 994 chromic acid, and oxidation of 149–152 chlorocholestenol 160 alcohols 1447 CD in achiral solvents 157 chlorochromate, pyridinium see chromium (IV), and oxidation of D/L nomenclature 149 PCC alcohols 1449 definition of 134 chlorocyclopropanone 185 chromium (VI) oxidation of helical 145 chloroform, and proton transfer alcohols 1447 and cyclophanes 145 351 kinetics 1449 induced chirality in achiral hydrolysis of 484 mechanism 1449 solvents 157 chloroformates, addition to chromium catalyst 309 NMR database 155 allenes 1005 chromium complex-Schiff base perpendicular dissymmetric benzyl, with amines 1240 complex 954 planes 141 SNi decomposition 440 chromium complexes 44, 116 torsional diastereomers 143 with alkenes 1005 chromium compounds, oxidation transfer 143 chlorofumaric acid, and of alcohols to carboxylic and [2,3]-Wittig asymmetric synthesis 165 acids 1492 rearrangement 1422 chlorohydrins, from epoxides and oxidation of aromatic truxilic acid 136 541, 997 hydrocarbons to quinones chloestenols 160 chloroimine, with ketenes, 1489 chloral 1095 enantioselectivity 1262 chromium hexacarbonyl 44 chloral hydrate 1095 chloromalic acid, and asymmetric chromium oxide, on silica gel Chloramine-T, and synthesis 165 1448 aminochlorination 1001 chloromethyl (1-)-4-fluoro-1,4- chromium reagents, and oxidative and formation of aziridines diazoniabicyclo[2.2.2] cleavage of alkenes 1470 1024 octane ditetrafluoroborate and oxidative cleavage of cyclic aziridine formation 1023 see Selectfluor ketones 1465 formation of aziridines from chloromethylation, and acidity chromium–salen complex, alkenes 1003 656 catalyst 1017 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1967

chromium tridentate-Schiff base Cinchonidine alkaloids, hydration Eschenmoser variant 1417 complex 954 and lactone formation 916 Eschenmoser-Claisen chromium trioxide, oxidation of cine substitution 774–775, 779 rearrangement 1417 aromatic hydrocarbons and aromatic nucleophilic ionic liquids 1416 1489 substitution 772 Ireland-Claisen 1417 chromium, oxidation states 1449 circuit resonance energy 57 Kimel-Cope rearrangement chromophore, absorption 318 circular dichroism 154 1417 definition 316, 318 and conformations 188 mechanism 1411, 1415 chromosome 318 chiral molecular in achiral Meerwein-Eschenmoser 1417 chromotropic spin traps 252 solvents 157 metal catalyzed 1416 chromous chloride, and iodoform vibrational 154–155 ortho rearrangement 1415 1070 circular polarization of para- 1415 and the Etard´ reaction 1479 luminescence 175 retro- 1415 CH oxidation of aryl methyl circularly polarized light 135, 157 substituent effects 1416 1479 and asymmetric synthesis 166 transition state 1415 oxidation, of alkenes, to allylic circulenes 50, 92 Claisen-Schmidt reaction 1173 alcohols 1478 circumambulatory rearrangements and aldol condensation Chugaev reaction 1304 236, 1403 1173–1174 and Ei reaction and mechanism cis-trans isomerism see isomers class e and class n reactions 1096 1305 cisoid conformation 1401 classification, of reactions by type and isotope effects 1305 cisoid diene 1036 of compounds synthesized CIDEP (chemically induced citric acid 184 1642 dynamic electron Claisen condensation 1183, 1253 clathrates 122 polarization) 253 See also Dieckmann and hydroquinone as host 124 CIDNP (chemically induced condensation hydrogen sulfide and dynamic nuclear and base strength 1255 pinacolone 123 polarization) 253 and chiral additives 1184 clay catalyst 525 alkylation of aromatic and Dieckmann condensation cleavage, oxidative see oxidative compounds 879 1254 cleavage, photolytic 319 and aryl radicals 846 and enolate anions 248, 580, cleavage, alkoxides 751 and bridged radicals 848 1253 ammonium salts 501 and formation of Grignard and Hunig’s¨ base 1253 anionic 751 reagents 748 and LDA 1183 aziridines 542 and intermediates 294 and microwave chemistry 334 aziridinium salts 542 and NMR 253 crossed 1253 bond, dissociative states 319 and organolithium reagents enantioselectivity 1184 carboxylic esters, with LiI 542 751 intramolecular 1253 cyanohydrins 751 and radical rearrangements mechanisms 1255 cyclic ethers 540 1348 metal catalysts 1183 Eschenmoser-Tanabe 1323 and radicals 253, 421, 1348 retro- 1254 Eschenmoser-Tanabe ring and SET mechanism 421 reverse 757 1324 and the photo-Fries Claisen reaction 1255 gas phase cleavage 240 rearrangement 676 Claisen rearrangement-Conia hydration of vinylidene nitriles and the Steven’s rearrangement reaction 1416 913 1382 Claisen rearrangement, thio- see Norrish Type I 326 carbenes 728 thio-Claisen Norrish Type II 327 Cieplak effect 906 Claisen rearrangement 1411, cleavage, of acetals, with Lewis Cinchona alkaloids, alkene 1414 acids 488 halogenation 994 abnormal 1419 of alkoxides 755 and alkyne anion acyl addition and allylic vinyl ethers 1415 of carbohydrates, catalyzed by 1144 and Carroll rearrangement NHC 981 and dihydroxylation 1008 1417 of cyclic thionocarbonates and Grob fragmentation 1322 and keto-enol tautomerism 1316 and Sharpless 1416 of diketones 757 aminohydroxylation 1019 and N-heterocyclic carbenes of diketones with base 757 and sulfinic esters 504 1416 of diols 1322 as chiral additive 960 and the Diels-Alder reaction of dioxetanes 1056 catalysts 976, 1186 1415 of epoxides, chiral halogenation of ketones 707 and the Willgerodt reaction B-halodiisopinocampheyl- chiral additive 1177 1605 boranes 541 with osmium catalysts 1006 catalysts 1416 of ethers 540 Cinchona-derived phase-transfer chair transition state 1415 with HBr or HCl 486 catalyst, epoxidation 1013 enantioselectivity 1416 structural parameters 1301 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1968 SUBJECT INDEX

cleavage, of acetals, with Lewis Complete neglect of Differential lumiflavin 1521 acids (Continued) Overlap 36 manganese, and with sulfuric acid 486 complexes, activated 285 dihydroxylation 1006 with thiolate anions 509 π-alkene 993 metal see metal complex of hydroperoxides 1576 alkene–metal 1517 metal–carbene 1426 of ketones, haloform reaction alkyne–mercuric salts 916 metal–salen, and epoxidation 757 and alkenes 116 1017 of oxonium ions 540 π-allyl 700 complexes, metals and π-donors of radicals 263 π-allyl palladium 564 114 of thioethers 884 π-allyl, mechanism 700 and benzene 115 peroxides 263 π-andη- 43 and cyclooctatetraene 116 photochemical, and radicals and carbon tetrahalides 116 and ferrocene 115 262 and cyclodextrins 127 and hapto complexes 114 aziridines 262 and π-encounter complexes 613 of cyclobutadienes 75 epoxides 262 and metal catalyzed optical resolution 146 reductive, of cyclopropanes decarbonylation of complexes, monohapto 115 1530 aldehydes 889 η- 43 strained cyclobutanes 1047 and π-arenium ions 611 η, and hydrogenation 1517 thermal, and radicals 261 and σ-arenium ions 608 d, π*-, organocuprates 964 thermal, cyclobutanes 1067 and SNAr π-reactions 770 organolithium reagents with ynones 1466 complexes, ate, borane with ethers boron compounds 964 Clemmensen reduction 1577 932 palladium peroxo 802 mechanism 1579 borate 736 Wacker process, mechanism clocks, radical clocks 850 complexes, bromine∙dioxane 645 1500 Clostridium sporogenes 1530 cage 127 π- 43 CO see carbon monoxide calixarene–proton 120 platinum, and resolution of Co-complexes 1017 channel-type 127 alkenes 168 Co–salen complex, charge transfer 114 quinone 116 halolactonization 999 UV, and solvents 473 radicals in aromatic solvents CO2 see carbon dioxide chlorine radical–solvent 857 856 cobalt catalyst, and cross coupling chromium 116 complexes, rate see rate 561 tridentate-Schiff base 954 complexes cobalt oxide nanocrystalline, cobalt–salen 999 rate 358 oxidation of alkanes 1477 π-complex and arenium ions ring-in-ring 128 cobalt salen 489 611 σ 114 coefficient, extinction 316 copper, and the Hay reaction σ-allylic copper(III) 563 coil reactors 1554 877 Schiff base–chromium 954 colchicinoid alkaloids, crown ethers 114 SnCl4–aldehyde and esters atropisomers 143 diastereomeric 168 368 collidine, and ester cleavage 542 EDA 114, 691, 1063 π-stability, table 612 Collins reagent 1448 electron donor–acceptor 114 with biphenyl 122 Collman’s reagent 602 charge transfer spectra 114 with crown ethers 117 and electrolysis 602 encounter 613 with cryptates 117 carbonylation 603 formation, and with fluoranthene 121 preparation of aldehydes or Fries-rearrangement 676 with hydrazine 124 ketones 602 complexes, Friedel-Crafts with picric acid 116 colloids, and sonochemistry 332 acylation 661 with pyrene 121 combinatorial chemistry 1244 Grignard reagents 245 with trinitrobenzenes 116 combinatorial library, amides guest–host 119 with urea 123 1246 hexacarbonyldicobalt–alkyne compounds, (CH)n, and Cope combustion, heat of 29, 32, 214 985 rearrangement 1414 common rings, strain 215 hydrides and carbonyls 1536 oxidation of side chains 1472 common-ion effects, and rate of hydrogen bonding 350, 356 Comprehensive Chemical Kinetics reaction 412 ion–dipole, and SN2 reactions 1626 communications, as a publication 409 Comprehensive Heterocyclic 1609 iron 116 Chemistry 1626 compatibility, functional groups iron, with cyclobutadienes 74 Comprehensive Medicinal and the Pauson-Khand iron, with norbornadienone 116 Chemistry 1626 reaction 986 Lewis acid–base 357 Comprehensive Organic Compendium of Chemical Lewis acid, and cleavage of Chemistry 1626 Terminology 1630 ethers 540 Comprehensive Organic Compendium of Organic Synthetic lithium acetylide– Functional Group Methods 1630 ethylenediamine 1144 Transformations 1626 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1969

Comprehensive Organic Synthesis acyclic compounds 188 axial and equatorial 195 1626 ae and eq nomenclature 197 chair-to-chair energy barrier Comprehensive Organic amides, torsional barrier 194 198 Transformations 1629 conformations, and acidity 368 chair-to-chair interconversion Comprehensive Organometallic and amides 194 195 Chemistry 1626 and atropisomers 194 cyclohexanes, and E2 reactions computational study, aldol-type and bisecting bonds 192 1278 reactions 1174 and conjugation 209 half-life 195 computer developed catalyst 310 and dihedral angle 193 observation of 195 concentration, and specific and dipole moment 190 conformations, cisoid 1401 rotation 135 and eclipsing bonds 192 cyclobutane 202 and structure of Grignard and epoxidation 1011 cyclodecane 203 reagents 246 and homoanomeric interactions cycloheptane 203 of radicals 252 200 cyclohexanone 199 concerted mechanisms 1382 and Meldrum’s acid 368 cyclohexene 199 concerted reactions, and SN2′ 443 and molecular mechanics 188 cyclopentane 202 Diels-Alder 1045 and Newman projections 189 envelope conformations 202 condensation, acyloin ester 1598 and NMR, of macrocycles 203 and half-chair conformations aldol see aldol and optical activity 188 202 benzoin 1215 and Pitzer strain 213 cyclopentanone 203 Claisen see Claisen and pK 368 cyclopropane 202 Dieckmann see Dieckmann and polar groups 200 cyclopropyl alkenes 209 self, and Claisen condensation and polarizability 190 conformations, definition 187 1253 and pseudorotation 203 diazoketones 1364–1365 Tollen’s 1600 and reactivity 379 conformations, dienes 1036 conducted tour mechanism 693, and silyl substituents 198 and Diels-Alder reactions 1039 699 and solvent 193 in the Diels-Alder reaction conducting polymers 392 and solvent effects 192 1036 configuration, absolute see and spectroscopic analysis 188 s-cis and s-trans 1036 absolute configuration and steric hindrance 194 conformations, dithianes 200 and carbocations 427 and strain 379 eclipsed 189 and Grignard reagents 247 and substituted cyclohexanes eclipsing 194 and sigmatropic migrations 196 enamides, torsional barrier 194 1405 and sulfoxides 203 energy, and cyclohexane 195 configuration, electron see and temperature 86 estimation of numbers 189 electron configuration and tetrahedral mechanisms ethane derivatives 191 of migrating group in 1092 ethanedial 193 sigmatropic and the E2 reaction 1276 formic acid 193 rearrangements 1405 and transannular strain 213 gauche 190–191 racemization of migrating group and X-ray crystallography 193 and butane 191 during rearrangement conformations, annulenes 78 and elimination 1279 1338 anomeric effect 200 and solvent effects 192 retention of migrating group anti 191 conformations, glucosides and the during rearrangement anti-periplanar, and E2 reagents anomeric effect 200 1338 1276 glycolaldehyde 193 and carbanions 243 anticlinal 190 heteroatom substituted rings of migrating groups 1338 antiperiplanar 190 199 configurational stability, % axial in substituted hydroxamic acids, torsional organolithium reagents cyclohexanes 199 barrier 194 243, 750 axial preference for polar in solid-state 220 configurations, definition 187 groups 200 isolation of conformers 192 conformational analysis 187–222 biaryls 195 lactones 203 conformational energy, butane bisecting 194 macrocyclic ketones 203 192 boat 195 medium-size rings 213 substituted ethanes 190 butane 191 MO calculations 368 conformational isomer, and butane derivatives 192 of dioxanes 200 conformer 188 caprolactams 203 orthogonal 195 conformational mobility, and carbamates, torsional barrier oxacyclooctane 203 hydrolysis 487 194 oxetane 202 annulenes 86–87 conformations, chair 195 pseudo-axial 204 conformational transmission 380 and bulky substituents 198 pseudo-equatorial 204 conformations, 3n rule 189 and carbocations 234 puckered 204 A1,3-strain 196, 1097 and gauche 197 s-cis, and dienes 1400 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1970 SUBJECT INDEX

conformations, glucosides and the of aldehydes, and microwaves and the Baylis-Hillman reaction anomeric effect 979 1149 (Continued) of allylic silanes 966 by dehydrogenation 1445 six-membered rings 195 of amines, enantioselectivity by the Knoevenagel reaction stability of 192 979 1187 aziridines 138 of boranes 967 with acyl halides 979 and optical activity 139 of phosphines 977 with aldehydes 1149 staggered 189, 191 of radicals 969 with sulfur ylids 1208 syn-periplanar, and E2 of silyl ketene acetals 967 conjugated dienes 720 reactions 1276 of thiols 978 conjugated ketones see ketones synclinal 190 organocuprates 961 alkylation 585 synperiplanar 190–191 organolithium reagents, metal and Nazarov cyclization 958 tetrahydrofurans 203 catalyzed 979 via Robinson annulation thioamides, torsional barrier organometallics 960, 963 reaction 1179 194 mechanism 963 conjugated systems, addition tub 146 photochemical 976 898 tub, cyclooctatetraene 146 radicals 969 alternant and non-alternant twist see twist conformations thiols 979 hydrocarbons 69 twist 195 trifluoroborates 969 dienes 898 and norbornane 196 vinylogous 957 conjugated-circuit model, and and twistane 196 conjugate, base, base in the E1 aromaticity 58 Wolff rearrangement 1364 reaction 1281 conjugation, and absorption conformers 188 definition 339 317 isolation of 192 LDA 1171 and bathochromic shift 318 Conia ene reaction 954 conjugate eliminations 1298 and carbanions 239 Conia reaction-Claisen conjugate reduction, and silanes and carbocations 227–228 rearrangement 1416 1528 and conformations 209 conjugate acid, definition 339 reagents for 1527 and cyclopropane 209 conjugate addition 895–896, 954 conjugate systems, and and delocalization 39 aldehydes with cyanide 979 delocalization 41 and dendralenes 44–45 amines 976 conjugated alkenes 698, 1289 and enol content 98 and anhydrides 979 and Baker’s yeast 1530 and homoconjugation 45 and conjugated aldehydes 956 enzymatic reduction 1530 and keto-enol tautomerism 98 and HMPA 980 frustrated Lewis pairs 1530 and radical stability 256 and ionic liquids 956 homogeneous hydrogenation and SN1 reaction 414 and microwave irradiation 976, 1529 and wavelength of light 317 979 hydrosilation, enantioselectivity cross see cross conjugation and phosphonate esters 979 1529 cross 44 and photolysis 969 miscellaneous reagents 1529 cyclobutanes and carbocations and the Sakurai reaction 966 reduction, Hantzsch ester 1527 229 and thioesters 979 hydride reducing agents cyclopropanes and carbocations boranes, metal catalyst 967 1527 229 N-heterocyclic carbene metal catalysts 1527 energy 42 catalyst 967 reagents 1526, 1528 heteroatoms with carbocations borates, organocatalysts 968 1,4-reduction 1527 230 boronates 968 transfer hydrogenation 1527 p orbitals with double or triple boronic acids 968 with silanes 1528 bonds 42 cyanides 991 with alkyl azides 1023 π- 891 diastereoselectivity 959 conjugated carbonyls, and bond simple, carbocations 227 diastereoselectivity, polarization 895 stabilization 42 organometallic compounds and hydride reagents 1533 conrotatory, and electrocyclic 962 epoxidation, mechanism 1015 rearrangements 1390 enantioselectivity 960 epoxidations 1015 conservation of orbital symmetry enolate anion 1179 isomerization 909 1050, 1358 conjugate addition, Grignard with nucleophiles 895 principle 1063 reagents 1129 with sulfur ylids 1205 constant, equilibrium see heteroaryl boronates 968 conjugated carboxylic acids see equilibrium heteroatom nucleophiles 975 carboxylic acids constant, rate see rate constant higher order cuprates 979 conjugated compounds, acylation constants, Planck’s 3 limitations of organocuprates 979 contact ion pair 415 962 addition of hydroperoxide contact ion-pair mechanism 693 Michael addition 954 anions 1441 continuous flow chemistry see of alcohols 977 and Stork enamine reaction 587 flow reactions JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1971

continuous liquid–liquid copper (I)-complexed rotaxane alkynyl acids, decarboxylative separation, and flow 131 coupling, metal catalyst chemistry 337 copper (III) complex, an 888 contorted aromatics 56 organocuprates 962 allylic carbonate 568 contra Friedel-Crafts alkylation copper complexes, and the Hay coupling, and Fenton’s reagent 649 reaction 877 874 cooperative hydrogen bonding copper catalyst 309 and Grignard coupling 562 108–109 coupling of alkynes 876 and ionic liquids 567 coordinate covalent bonds 17 Gomberg-Bachmann-Hey and organometallics 882 coordinate, reaction 285 reaction 832 and triflates 562 coordination number 9 copper compounds, with aryl halides, metal catalyzed Cope elimination 1297, 1307 organolithium reagents coupling 562 and ammonium salts 1383 555 aryldiazonium salts with active and Cope rearrangement 1408 copper salts, and alkyne coupling methylene compounds aza- 1308 876 710 Ei mechanism 1307 and the Glaser reaction 876 carbonylative cross 561 isotope effects 1296 copper, alkyl–magnesium bromide cross see cross coupling mechanism 1307 Normant reagent 951 cross, radical coupling of polymer bound 1308 corannulene 91–92 alkanes 874 rate of reaction 1307 Corey-Seebach procedure 1108 definition 544 solvent effects 1307 hydrolysis of dithioketals 1110 diazonium 610 Cope rearrangement, amino see Corey-Winter reaction 1316 diazonium salts and aromatic amino-Cope Cornforth model, and asymmetric compounds 638 Cope rearrangement, aza- see synthesis 163 enolate anions, Pd catalyzed aza-Cope and diastereoselectivity 163 565 Cope rearrangement 1408, 1415 Corporate Index 1638 flow reactions, Pd catalyzed and 1,5-dienes 1409 correlation diagram method 1045 565 and bullvalene 1412 coulombic interactions, and Grignard reagents 551, 880 and Cope elimination 1408 molecular mechanics 204 heteroaromatic compounds and density functional theory coumarins, and the Pechmann 658 1409 condensation 654 coupling, malonate anions, Pd and NMR 1412 counteranion-controlled catalyzed 564 and organocatalysts 1409 disulfonimide Mannich bases 567 barbaralane 1413 organocatalyst 967 metal catalyzed 564 boat transition state 1410 counterattack reagent 544 Suzuki-Miyaura coupling (CH)n compounds 1414 counterions, and ambident 801 chair transition state 1410 nucleophiles 481 mechanism 562 degenerate 1412 and nucleophiles 481 with silanes 545 density functional theory 1409 of carbocations 225 Negishi 561 diene stability 1409 solvation 461 of carbenes 273 divinyl oxiranes 1410 coupling constants 19 of photosensitized alkanes divinyl phosphiranes 1410 and hydrogen bonding 110 874 divinyl thiiranes 1410 coupling, alcohols 568–569 of radicals 263 1,5-diynes 1410 and Grignard reagents 568 organolithium reagents 551 fluxional structures 1412 metal catalyzed 568 with sulfones 567 hypostrophene 1413 with organolithium reagents organometallic reagents 567 infinitely degenerate 1412 569 with alcohols 568 mechanism 1411 coupling, alkanes 724 with alkyl halides 558–563 metal catalyzed 1410 alkyl aryl 560 oxidative see oxidative non-concerted 1411 coupling, and indium 562 coupling radicals 1412 alkyl halides 549 palladium, catalyzed reversibility 1409 and radicals 563 intramolecular 566 semibullvalene 1413 metal catalyzed coupling 562 allylic acetates 566 shift equilibrium 1409 alkyl organometallics and vinyl allylic carbonates 566 six-centered pericyclic process halides 719 and ionic liquids 565 1410 alkyl tosylates 560 Knoevenagel-type stereochemistry 1410–1411 alkylboranes, silver catalyzed carbanions 565 thermodynamic stability of 882 pinacol see pinacol dienes 1409 alkyltrifluoroborates 809 coupling, radical 845 transition state 1409 alkyne, and trifluoroborates and the Kolbe reaction 885 Cope, oxy- see oxy-Cope 878 of amides 874 copper–quinoline decarboxylation, chiral ligands 818 coupling, reactions 874 mechanism 684 metal catalyzed 878 cross-coupling 545 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1972 SUBJECT INDEX

coupling, reductive 1593 crown ethers, acyl halides with cuprates see organocuprates SET mechanism 567 amines 1313 cuprates 444 silanes, allylic 875 and acylation of amines 1241 silyl 563 with alkyl halides 545 and decyanation 760 with acetylenic sulfoxides 962 SN2′ reactions, palladium and elimination reactions 1279 cuprous cyanide 600 catalyzed 565 and ion pairing in elimination and halides, aryl, in ionic Suzuki-Miyaura 798 reactions 1280 liquids 794 symmetrical, alkyl halides 551 and kinetic resolution 169 with aryl diazonium salts 828 unsymmetrical 563 and preparation of alcohols Current Abstracts of Chemistry vinylboronic acids 801 from amines 505 and Index Chemicus 1625 with alkylboronic acids 559 chiral 118, 169 Current Chemical Reactions 1625 Wurtz reaction 554, 549 complexes 114 Current Contents 1614–1625 covalency, C—Li bond 749 Gabriel synthesis 530 Current Contents Connect 1614 covalent bonds, and soft acids and resolution 167 Curtius reaction 532 bases 360 with KMnO4 1470 Curtius rearrangement 1338, covalent compounds, and with metals, and decyanation 1364, 1371 electronic structure 16 760 and Lewis acid catalysis 1371 Cram’s rule 1088 with permanganate, oxidative mechanism 1371 and asymmetric synthesis 162 cleavage of alkenes 1470 migratory aptitudes 1340 and diastereoselectivity 162 cryptands 119–121 Arndt-Eistert synthesis 1364 and reactions at carbonyls and phase transfer catalysis 476 cyanamides, addition of ammonia 1088 and resolution 169 1126 and reduction of ketones 1546 and solvation 461 from tertiary amines 544 CRC Handbook of Data on organolithium reactions 1135 hydrolysis 1101 Organic Compounds 1621 cryptate ions 476 with amines 522 cresol, dipole moment 20 cryptates 119, 183 cyanates, from alkyl halides and Criegee mechanism, and ion pairs and complex formation 117 isocyanate 479 1467 and out–in isomers 182 cyanates, halo 999 ozonolysis 1467 cryptophanes 120 cyanation 723 critical temperature, and carbon crystal structures, hydrogen bonds cyanation, and ion radicals 724 dioxide 392 112 metal catalyzed 723 cross conjugation 44 crystallization, fractional, and nitro compounds 724 and bond distance 45 resolution 166–172 of alkanes 723 and trienes 45 Grignard reagents 246 of aromatic compounds 672 cross coupling, cobalt catalyst seeding method 171 of carbonyl compounds 723 561 crystallographic scale, acidity 346 with copper catalysts 795 iron catalyst 561 crystals, and mechanical cyanides, acyl formation of, nickel catalyst 561 resolution 170 mechanism 1256 with alkynes 597 liquid see liquid crystals from esters and nitriles 1256 cross metathesis, alkynes 1430 radicals 257 cyanides, ambident nucleophile cross-coupling see coupling CS2 see carbon disulfide 600 cross-metathesis 1429 cubane 1431 and isonitriles 600 cross-coupling reactions 545 and strain 211 aryl, conversion to arylsilanes Grignard reagents 553 rearrangement 1431 547 cross-dimerization, of alkanes cubene 221 as an ambident nucleophile 480 875 cubycarbinyl radicals, conjugate addition 991 crossed, acyloin condensation rearrangement 265 cuprous, with aryl halides 794 1598 cubyl carbocations 232, 234, 413 from organometallics 743 Cannizzaro reaction 1193, and ab initio calculations 413 hydrolysis 295 1601 and SN1 reactions 413 metal, with alkyl halides 600 Claisen condensation see cubylcarbinyl radicals 1347 Michael reactions 958 Claisen cucubituril gyroscane 131 potassium, and the benzoin pinacol coupling 1595 cucurbit[8]uril rotaxanes 132 condensation 1216 Tischenko reaction 1602 cucurbiturils 131–132 reaction with epoxides 601 crossover experiments 405 and luminescence 132 tetrabutylammonium 601 and Fries rearrangement 676 cumene hydroperoxide, homolytic tosyl 600 and rearrangement 1336 cleavage 840 tosyl, with enolate anions 723 and SN2 reactions 407 cumulenes, and optical activity trimethylsilyl see trimethylsilyl and Fries rearrangement 676 145 cyanide crotylmercuric bromide, with HCl cyclic 216 trialkylsilyl 600 695 from dihalides 1319 vinyl, from vinyl halides 600 crowding, intramolecular 220 via 1,4-elimination 1319 with aldehydes 980 crown ethers see ethers cuneane 1431 and conjugate addition 979 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1973

with aldehydes or ketones 1212 cyclic compounds, and cis/trans and the Woodward-Hoffman biocatalysts 1210 isomers 179 rules 1080 with alkyl halides 480, 599 and I strain 379 benzene derivatives 1312 with aryl nitro compounds cyclic cumulenes 216 Diels-Alder 1035–1055 834 cyclic epoxides 1056 Huckel¨ system 1048 with bisulfite addition product cyclic ethers see ethers, cyclic Huckel-M¨ obius¨ rules 1048 1211 cyclic groups, and solvolysis 455 Huisgen 1033 with epoxides, metal catalyzed cyclic imides 1241 of 1,3-dipoles 1027–1035 601 cyclic intermediate mechanism of alkenes to alkenes with organocopper reagents 1464 1056–1067 744 cyclic mechanism 898 other 1079 with sulfates 600 and the Prins reaction 1214 photochemical 1055 with sulfonates 600 reduction of hydrazones 1578 [1+2]-cycloaddition reactions, and cyano acids, decarboxylation cyclic molecules, and entropy 284 carbenes 1067 752 cyclic resonance energy 61 [2+2]-cycloaddition reactions cyano group, reduction to methyl, cyclization, addition of alkenes to 1046 with terpenes 1566 alkenes 942 addition 1056–1067 cyano-ketones, displacement of alcohols, with carboxylic acids allenes 1057, 1066 cyano 568 1230 allowed and forbidden 1063 cyanoacetates, with boronic acids aldehydes or ketones with and entropy 1064 724 amines 1113 and orbital symmetry 1064 cyanoamines, formation, alkene amides 1027 and photosensitizers 1060 enantioselectivity 1212 alkyne–acids 1027 and valence isomers 1063 from addition of HCN to C=N alkynes to alkenes 943 concerted mechanism 1059 compounds 1212 amidation of alkenes 930 diion mechanism 1065 from amines 724 and Dieckmann condensation enamines 1058 cyanobacterial aldehyde 1253 enol ethers 1058 decarbonylase 889 and extrusion reactions 1331 exo/endo ratio 1064 cyanoborohydride, reduction of and neighboring group effects flow reactions 1060 alkyl halides 1568 425 forbidden reactions 1063, 1396 sodium, and reduction of alkyl the Thorpe reaction 1209 forbidden, and metal catalysts halides 1569 and the Thorpe-Ziegler reaction 1396 cyanocuprates 962 1209 formation of β-lactams 1058 cyanogen bromide 544 Bergman 1395 intramolecular 1059 and isotopic labeling 295 by acyloin condensation 1598 ketenes 1057 with amines 544 en-ynes, metal catalyzed 985 ketenes with cyclopentadiene with carboxylate salts 1260 Friedel-Crafts 654 1064 cyanohydrins 980 halogenation of homoallylic β-lactams 1263 and lyase catalysts 1210 alcohols 997 masochistic steric effects 1066 and Mannich reaction 1211 hydroformylation 990 mechanism 1059, 1062–1064 and Strecker synthesis 1211 intramolecular 939 metal catalyzed 1057, 1059 and the benzoin condensation Johnson polyene 944 organocatalysts 1059 1210 Nazarov 958 Paterno-Buchi¨ reaction- 1060 cleavage 751 of aldehydes 981 photochemical 1062 conversion to diketones 980 of alkene–acids, and Woodward-Hoffmann enzyme catalysis 1211 enantioselectivity 1026 rules 1063 formation of HCN 991 of dienes 944 diradical mechanism 1060 from aldehydes or ketones of diynes, metal catalyzed 943 formation of oxetanes 1060 1210 of enynes, metal catalyzed 945 photochemistry 1057 hydrolysis 1100 of organolithium reagents 948 radicals, mechanism 1059 cyanomethanes, pKa 363 of radicals 421 stereochemistry 1059 cyanomethylamines 723 of triflamide alkenes 931 steric interactions 1064 cyanonitrene 715 organolithium reagents with stereospecificity 1066 cyanuric acid, conversion to alkenes 947 structural variations 1057 Formate esters 1234 photochemical 327 thermal 1059 cyanuric fluoride, with carboxylic Prins reaction 1214 thioenol ethers 1058 acids 1251 radical see radical cyclization ylids with carbonyls cyclams 367 radical, to aldehydes 1217 compounds 1199 cyclazines, and antiaromaticity 86 Rauhut-Currier 1151 [2+2+1]-cycloaddition reactions cyclic amines, from halo-amines cycloacenes 85 1083 515 cycloaddition reactions 1081 [2+2+2]-cycloaddition reactions cyclic anhydrides, Friedel-Crafts 1,3-anionic 1034 1077, 1081, 1083–1084 acylation 660 and microwaves 336 metal catalyzed 1081, 1083 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1974 SUBJECT INDEX

[2+2+2+1]-cycloaddition [4+4]-cycloaddition reactions cycloreversion 1067 reactions 1085 1080 divinyl, rearrangement 1410 [2+2+2+2]-cycloaddition [4+4]-cycloaddition reactions from ketenes 1057 reactions 1085 1081 pyrolysis 209 [3+1]-cycloaddition reactions [4+4+4]-cycloaddition reactions [2+2]-ring opening 1431 1079 1080–1082 strained, cleavage 1047 [3+1+1]-cycloaddition reactions [5+1]-cycloaddition reactions thermal cleavage 1067 1084 1080 vinyl, rearrangement 1407 [3+2]-cycloaddition reactions [5+2]-cycloaddition reactions cyclobutanones, extrusion of 1027–1035 1080–1081, 1085 carbon monoxide 1331 alkenes with allenes 1035 [5+2+1]-cycloaddition reactions from diazonium salts 1408 all carbon 1033 1085 photolysis 1331 allylic carbocations 1035 [6+2]-cycloaddition reactions cyclobutene ring opening, Huckel¨ and allylic carbanions 1034 1080–1081 system 1392 and Dewar benzene 1063 [6+3]-cycloaddition reactions cyclobutene–diene and Diels-Alder 1029 1080 interconversion, orbital and diradicals 1034 [6+4]-cycloaddition reactions requirements 1392 and FMO 1031 1080, 1082 cyclobutenes, conrotatory ring and LDA 1035 cycloadducts, [3+2]-cycloaddition, opening, and HOMO and photocatalysts 1034 unstable 1031 symmetry 1392 antibody catalyzed 1035 cycloalkadienes, via Cope from alkenes with alkynes diazoalkanes 1032 elimination 1308 1067 diionic intermediates 1031 cycloalkanes, and strain 214 from cyclic sulfones 1332 dipolar compounds 1029 heat of combustion, table 214 from cyclopropylcarbenes 273 enantioselective 1032 cycloalkenes, and chiral axis 152 from methylenecyclopropanes flow reactions 1031 and strain 216 1357 formation of cyclopentanes cycloalkynes, and platinum HOMO, and photochemistry 1033 complexes 216 1391 fulminic acid 1031 and strain 216 orbitals, and thermal ring hydrazones 1028 cycloamyloses see cyclodextrins opening 1392 intramolecular 1033 cyclobutadienes 73 ring opening, torquoselectivity intramolecular, metal catalyzed and antiaromaticity 73 1390 1034 and aromaticity 70, 73 thermal ring opening 1393 ionic liquids 1032 and carcerands 73 thermal ring opening to dienes mechanism, nonsynchronous and low-temperature matrix 73 1389 1031 and NMR 74 cyclobutyl, and nonclassical metal catalysts 1032 and steric hindrance 74 carbocations 436 retro 1031 and strain 74 and rate enhancement 438 stereoselectivity 1031 and X-ray 74 as neighboring groups 430 structural variations 1032 antiaromaticity 39 carbocations 229 trimethylenemethane 1034 derivatives, and the captodative compounds, and solvolysis with nitrile oxides, in effect 74 436 supercritical CO2 1032 derivatives, NMR 74 dication 72 [3+1+1]-cycloaddition reactions, dideuterio 73 from cyclopropylmethyl 437 Lewis acid catalyzed 1084 Diels-Alder reaction 73 cyclobutylcarbinyl radical see [3+2+1]-cycloaddition reactions, enthalpy 73 radicals reactions 1084 infrared 73 cyclocarbopalladation 548 [3+2+2]-cycloaddition reactions iron complex 74 cyclodecane, conformations 203 1085 isomers 73–74 cyclodecapentaene, and [3+3]-cycloaddition reactions metal complex 74–75 aromaticity 71 1079 aromaticity 74 cyclodehydration 500 [3+4]-cycloaddition reactions MO calculations 73 and Friedel-Crafts alkylation 1031 PES 73 653 [4+1]-cycloaddition reactions stable derivatives 74 cyclodextrins 125–126, 497, 522 1080 synthesis of 73 and cage complexes 127 [4+2]-cycloaddition reactions see cyclobutanes, and bromine 209 and channel-type complexes Diels-Alder and pyrolysis 209 127 [4+2+1]-cycloaddition reactions and strain 208–209 and complex formation 127 1085 angle strain 209 and formation of [4+2+2]-cycloaddition reactions by [2+2]-cycloaddition 1058 amino-alcohols 523 1085 conformations 202 and resolution 169 [4+3]-cycloaddition reactions conjugation with carbocations and water solubility 126 1080–1081 229 capped 127 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1975

catalysts, esters, hydrolysis from phenols 1524 cyclopentanes, by 1219 from vinylcyclobutanes [3+2]-cycloadditions 1034 cavity 126 1407 conformations 202 cyclodiastereomerism 130 cycloisomerization 914, 944 energy barrier to planarity 203 cyclodibromodi-μ-methylene[μ- hexahydro-Diels-Alder methylene 1034 (tetrahydrofuran)]trizinc 1043 via [3+2]-cycloaddition 1033 see Nysted reagent cyclononyne, and strain 216 conformation 203 [2+2]-cycloelimination 1263 cycloocta-1,2-diene 217 cyclopentanyl cation 76 cycloenantiomerism 130 cyclooctadiene-diynes 77 cyclopentenes, by rearrangement cycloheptadiene 216 cyclooctadienes 216 of vinylcyclopropanes cycloheptane, conformations 203 preparation of 9-BBN 934 1406 cycloheptatrienes-norcaradiene, with iodine 214 cyclopentenone, valence tautomerism 1414 cyclooctadienones 1417 photodimerization 330 cycloheptatrienes, and aromaticity cyclooctatetraenes 76, 116 cyclopentynes 1349 64 and aromaticity 71, 76 and strain 216 from carbenes 1073 and chirality 146 cyclophanes 50, 88 See also with alkynes 1081 and metal complexes 116 paracyclophanes cycloheptatrienide anion 77 and strain 77 cyclophanes, and a chiral axis cycloheptatrienyl cations see conformation and bond angles 152 tropylium ion 77 and anisotropy 55 cations 65 dehydrohalogenation 77 and aromaticity 50 cycloheptatrienyl anions, ad dications 67 and chirality 145 aromaticity 77 in sulfuric acid 90 and pseudorotation 51 antiaromaticity 77 NMR 76 and ring current 56 cycloheptatrienyl derivatives, and by cyclization of octatetraenes belt 50 NMR 77 1396 cyclopolyacenes 85 cycloheptynes 216 cyclooctenes, and chirality 146 cyclopropabenzene 51 cyclohexaamylose 127 and cis/trans isomers 177 cyclopropanation, and carbenoids cyclohexacenes 85 photoisomerization 328 1075 cyclohexadiene ring opening trans, and chirality 145 and carbenoids, 1394 double bond 216 enantioselective 1075 cyclohexadiene–hexatriene resolution of 168 and sulfur ylids, interconversion 1394 strain energy 218 enantioselectivity 1207 cyclohexadienes 1324 cyclooctynes, and strain 216 by metal catalyzed diazoalkane from benzene 1525 heat of hydrogenation 216 reactions 1068 from Diels-Alder reactions infrared 216 flow reactions 1072 1041 cyclopentadienes, and annellation heterocycles 1073 rearrangement 1361 64 indoles 1073 cyclohexadienones, and and circumambulatory metal catalyzed 1073 tautomerism 101 rearrangement 1403 of alkenes 1070 rearrangement 1360 and hyperconjugation 96 enantioselective 1072 photochemical rearrangements and metallocenes 66 metal catalyzed 1071 1433 derivatives, pKa 64 of alkynes 1072 cyclohexane derivatives, pKa 63 of aromatic rings 1073 stereoisomers 180, 198 [1,5]-sigmatropic organocatalysts 1072 cyclohexane-1,2-diols 351 rearrangements 1403 pyrroles 1073 cyclohexanediol, disubstituted with ketenes, cyclopropanediazonium ions 201 [2+2]-cycloaddition 639 cyclohexanes, A1,3-strain 196, reactions 1064 cyclopropanes 75 1097 with ketenes, orbital overlap addition reactions 906 alkylidene, and chirality 145 1065 and bent bonds 209 and equilibrium 195 cyclopentadienide ion 63–64 and bond angles 208 and stereochemistry 160 and aromaticity 62 and bromine 208 conformations 195 canonical forms 63 and conjugation 209 pseudorotation 195 diatropic 64 and diradicals 1358 substituted, conformations 197 resonance energy 63 and electron density 208 cyclohexanones, cleavage to adipic cyclopentadienones 65 and hydrogen bonding 111 acid 1465 cyclopentadienyl anion 76 and MO calculations 208 conformations 199 cyclopentadienyl cation, and and photochemistry 1530 cyclohexapeptoids 476 aromaticity 75 and sigmatropic shifts 1404 cyclohexenes, aromatization 1442 nonaromatic and aromatic 76 and stabilization of bond energy 37 preparation and diradical carbocations 426 conformations 199 character 76 and UV 209 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1976 SUBJECT INDEX

cyclopropanes, by carbene with HBr 906 cyclopropylmethyl carbocations transfer 1068 with nitrones 1033 229 by [1+2]-cycloaddition 1067 with bromoalkynes 599 and NMR 437 by extrusion of nitrogen from cyclopropanones, by photolysis of cyclopropylmethyl groups, and pyrazoles 1330 cyclobutanones 1330 carbocations 436 by extrusion of nitrogen from from ketenes 1070 and nonclassical carbocations pyrazolines 1330 intermediate, Favorskii 436 carbene addition to alkenes rearrangement 1362 cyclopropylmethyl, and rate 1067 trapping, Favorskii enhancement 438 catalytic hydrogenation, metal rearrangement 1363 and rearrangement 437 catalysts 1530 cycloproparenes 51 and solvolysis 436 conjugation with carbocations cyclopropenes 75, 215 and σ-bond participation 436 229 and hydrogen exchange 75 formation of cyclobutyl 437 conversion to gem-dimethyl and strain 215 cycloreversion, of cyclobutanes groups 1531 by extrusion of nitrogen from 1067 dihalides, carbene formation pyrazolines 1330 cyclotrimerization, triynes, 1358 by extrusion reactions 1331 structural variations dihalo 1070 from alkynes 1072 1078 with organolithium reagents cyclopropenium carbocations and ring expansion 1079 1359 230 and the Diels-Alder reaction divinyl, rearrangement 1410 cyclopropenium diazonium salts 1079 from carbenes 1070 467 boronic esters 1077 from conjugated carbonyl cyclopropenium intermediate of alkynes, aromatic compounds 1205 496 compounds 1076 from ketenes 1070 cyclopropenones 72, 1073 solid-supported 1077 from pyrazolines 1032 cyclopropenyl anions 237 sonication 1077 from sulfur ylids 1205 and aromaticity 75 triynes 1077 from sulfur ylids and conjugated cyclopropenyl cations 76 mechanism 1078 compounds 1208 and aromaticity 72 metal catalyzed 1078 cyclopropanes, hydroacylation, cyclopropyl alkenes, with metal carbenes, formation N-heterocyclic carbene conformations 209 of heterocycles 1079 catalysts 980 cyclopropyl alkynes, and radicals cysteine and cystine, hydrogenation, formation of 256 interconversion 1510 gem-dimethyl groups cyclopropyl anions 243, 1397 cysteine–cystine, interconversion 1531 cyclopropyl carbocations, and ring 1510 intermediates 1339 opening 1397 isomerization, carbene cyclopropyl groups, and d orbitals 16 See also orbitals intermediates 272–273 carbocations 229 overlap, carbanions 693 orbital overlap 209 and solvolysis 455 d, π*-complex, organocuprates orbitals 209 cyclopropyl, and anchimeric 964 photolysis, and carbenes 270 assistance 429 D2, and catalytic hydrogenation protonated, and rearrangements as a neighboring group 429 1519 1339 homoconjugation 46 D2O, and the Cannizzaro reaction pyrolysis 208, 1358 ring opening 1397 1602 radicals 260 cyclopropylbenzenes, from allyl DABCO 182 cyclopropanes, reaction with benzenes 1432 and aza-Baylis-Hillman carbocations 907 cyclopropylboronate, from reaction 1166 with radicals, mechanism 908 cyclopropane derivatives and Morita-Baylis-Hillman cyclopropanes, reductive cleavage 937 alkylation 1151 1530 cyclopropylcarbinyl see and preparation of aryl ring opening 598 cyclopropylmethyl boronates 793 ab initio studies 907 cyclopropylcarbinyl carbocations and the Baylis-Hillman reaction conrotatory versus see carbocations 1149 disrotatory 1397 cyclopropylcarbinyl radicals see daisy chains 128 mechanism 1357 radicals Dakin reaction 1473 cyclopropanes, solvolysis 1398 cyclopropylcarbinyl carbocations and Baeyer Villiger reaction stabilization of carbanions 240 426 1473 strain 208 cyclopropylcarbinyl radicals 264 in ionic liquids 1474 to propene, and entropy 286 as radical clock 264–265 mechanism 1473 via sulfur ylids 1205 rearrangement, metal catalysts Dakin-West reaction 756 vinyl see vinylcyclopropanes 1357 dammaradienol 944 from dienes 1432 cyclopropylmethyl see Danishefsky’s diene 1052 with amines 526 cyclopropylcarbinyl Darzan’s, aza 1191 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1977

Darzens condensation 1190 dealkylation, of amides 1592 of aryl carboxylic acids 683 and halo substrates 1190 of amines 1591 of bridgehead keto-acids 752 and Knoevenagel reaction 1190 reagents 1592 of carboxylate ions 752 aza- 1191 of sulfonamides, reagents 1592 of carboxylate salts, with diastereoselectivity 1191 deamination, of amines 1580 cyanogen bromide 1260 enantioselectivity 1191 Dean’s Handbook of Organic of carboxylic acids 751 functional group compatibility Chemistry 1620 of conjugated acids 755 1191 debyes, and dipole moment 20 of cyano acids 752 mechanism 1190 decahydroquinazolines 103 of esters 753 structural variation 1191 tautomerism 103 elimination, Ei, mechanism Darzens glycidic ester synthesis decalin, cis/trans isomers 180 1304 see Darzens condensation decalol, and borane 1386 to alkenes 1303 DAST (diethylaminosulfur decarbonylase, cyanobacterial to alkenes, solvent free 1304 trifluoride), fluorination of aldehyde 889 of fatty acids 754 sulfoxides 709 decarbonylation, acyl halides 754 of glycidic acids 753 with acyl halides 1251 and peroxides 889 of keto esters 753 fluorination of alcohols 539 and photolysis 889 of keto-acids 752 formation of gem-difluoro and radicals 889 of β-lactones 1331 compounds 1128 metal catalyzed, of acyl halides of malonic acids 751, 1236 with aldehydes or ketones 1128 to alkenes 1315 of radicals 874 databases, CAS 1633 of acyl halides 889 of glycidic acid, mechanism Davies catalyst 308 of aldehydes 327, 1346 753 DBN, and elimination 1311 metal catalyzed 888 of silver carboxylates 886 and carbonylation of aryl mechanism 889 decarboxylation, oxidation, metal halides 821 with Wilkinson’s catalyst catalyst 1474 and elimination 1311 889 oxidative 1474 and malonic ester synthesis 577 of aryl aldehydes 683 of carboxylic acids to alkenes and NBS, with carbamates SE1 mechanism 683 1474 1371 decarboxylation 293 of carboxylic acids, and thioethers 507 and boric anhydride 754 mechanism 1474 catalyst, and aza-Michael and Bredt’s rule 752 photochemical 684, 752, 754 reaction 976 and carbanion formation 249 rate of reaction 755 urea–hydrogen peroxide 1016 and labeling 684 SE1 mechanism 685, 755 DBU 182 and microwaves 753 SE2 mechanism 755 DCC (dicyclohexylcarbodiimide) and quinoline 684 six-center mechanism 752 712, 1231 and silver acetate 684 structural limitations 753 amines with CS2 1127 and solvent effects 755 structure and carboxylic acid and DMSO 1451 and the arenium ion mechanism reactivity 753 and Moffatt oxidation 1451 683 decarboxylative alkylation 755 and thioalkylation 671 and the Dakin-West reaction arylation 755 carboxylic acids with H2O2 756 fluorination 491 503 and the Hunsdiecker reaction Nazarov cyclization 958 DDQ, and aromatization 1443 886 of ketones 585 and cleavage of ethers 540 and the malonic ester synthesis Strecker synthesis 1212 and formation of azides 531 576 decomposition, of acyl azides dehydrogenation 1446 and the SE1 mechanism 683 1336 oxidation of alcohols 1456 decarboxylation, Barton, and of chloroformates 440 deactivated aromatic rings, and ultrasonic flow conditions of diazonium salts 826 Friedel-Crafts acylation 755 of peroxides 840 659, 669 conjugated carboxylic acids of radicals 263 deactivating groups, and multiple 755 decyanation, and crown ethers substituents 622 Krapcho 753 760 for aromatic substitution 776 mechanism 752 and radicals 760 in aromatic compounds 614 metal catalyzed 683, 754 of nitriles 760, 1584 in SNAr reactions 776 decarboxylation, of alkynoic acids dediazoniation, of aryldiazonium deactivation, in photochemistry 754 salts, mechanism 1587 325 of allylic acetates with reagents 1587 DEAD (diethyl azodicarboxylate) keto-acids 887 of diazonium salts 1587 1510 of allylic carboxylic acids 754 deep eutectic solvents 395 and carboxylate salt alkylation of amides, to alkenes 1304 and Grignard reactions 1130 501 of amino acids 754 and Williamson ether synthesis and decarboxylation 1323 of aromatic acids 755 490 and the Mitsunobu reaction 495 of aryl acids 752 ionic liquids 395 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1978 SUBJECT INDEX

deep eutectic solvents (Continued) and photochemistry 1446 density functional theory 78, 410 organolithium reactions 1130 catalytic, and oxidation of and the Cope rearrangement urea–choline chloride 497 alcohols 1454 1409 definition, Markovnikov’s rule formation of quinolines 1446 deoxycholic acid, as host 902 metal catalyst 1445 124–125 defluorination, aryl fluorides 1570 N-heterocyclic carbene deoxygenation, of alcohols 1574 deformation, of aromatic rings, catalyzed 1249 of phenols 1572 and strain 624 of aldehydes or ketones 1446 of aldehydes or ketones 1577 degenerate carbocations 1337 of amines 1445, 1461 reagents 1578–1579 degenerate Cope rearrangement to nitriles 1460 silanes 1578 1412 remote 1446 of diols 1315–1316 degenerate rearrangements 1337 with DDQ 1446 of epoxides 1531 dehalogenation, and Friedel-Crafts with triphenylmethyl cation of sulfoxides 1591 catalysts 1569 1446 of sulfoxides, isotope labeling of acyl halides to ketenes, metal dehydrogenative Diels-Alder 1591 catalyzed 1320 reaction 1043 deoxyribonucleic acids see DNA of alkyl halides 1567 Dehydrogenative deprotometalation, aromatic 685 of aryl halides 1569 heteroatom-Diels-Alder deprotonation, and pKa 575 mechanism 1570 reactions 1054 of arenium ions, and steric photochemical 1570 Dehydrohalogenation 77 hindrance 610 of dihalides 1319 and non-ionic bases 1312 of carbonyl compounds, of heteroaryl halides 1570 and Hoffmann’s rule 1312 deprotonation 579 dehydrating agents 1236 and organolithium reagents to from carbanions 249 alcohols, with carboxylic acids 1313 with Grignard reactants 733 1231 and phase transfer 1312 with organolithium reagents and esterification of acids 1229 and photochemistry 1312 733 for amides to isonitriles 1328 and Zaitsev’s rule 1312 with organometallics 733 for dehydration of alcohols by pyrolysis 1313 with Weinreb amides 580 1299 Ei mechanism 1313 deracemization, and resolution molecular sieves 1229 mechanism 1313 172 silica gel 1229 metal catalyzed 1312 and Sphingomonas dehydration, acid catalyzed, of of alkynes 1312 pauchimobilis 172 alcohols 1299 dehydrosulfenylation 1304 biochemical 172 and the von Braun reaction dehydrosulfurization reagent 533 Dess-Martin periodinane 488, 532 1327 Delepine´ reaction 515 and halogenation of ketones of alcohols 495 delocalization energy, aromaticity 708 and aldol condensation 1299 index 57 and ionic liquids 1454 and Hofmann’s rule 1299 delocalization index, Bader’s 64 and oxidation of alcohols 1453 and Zaitsev’s rule 1299 delocalization, and bond distance stability and sensitivity 1453 dehydrating agents 1299 39 destabilizing groups, and mechanism 1300 and bond length 56 carbocations 454 with metal catalysts 1300 and butadiene 41 desulfurization 1589 of amides 1327 and carbocation structure 227 by catalytic hydrogenation 884 of carboxylic acids 1304 and conjugated systems 41 by Raney nickel, and the of diols 1300 and hyperconjugation 44, mechanism 1589 of halohydrins 1300 93–94 by samarium in acid 884 of oximes 1325 and nonclassical carbocations mechanism 1589 of nitriles and microwaves 425 of aromatic rings, mechanism 1325 and vinyl chloride 42 1589 of ureas 1328 migrating aryl radicals 1347 of dithianes 1589 reagents, amides to nitriles table of acids 753 of dithioacetals 1588 1327 type, and valence structures of dithioketals 1110 reagents, for ureas 1328 227 of dithiolanes 1589 dehydro[26]annulenes 83 delocalized bonding 33 of heterocycles 1588 dehydroannulenes 76, 83 delocalized bonds 39, 41 of sulfones 1588 reactions 81 delocalized carbocations, table of sulfoxides 1588 dehydrobenzenes see benzynes 228 of thioethers 883, 1588 dehydrobenzo[22]annulene 83 demethylation, of alkaloids 1592 of thiols 883, 1588 dehydrobenzoannulenes 82–83 of quaternary ammonium salts of thiophenes 884, 1588–1589 dehydrogenase, glycerol-3- 509 to methylene units 1589 phosphate 1435 Demyanov rearrangement 1357 with hydride reagents 1588 dehydrogenation, and dendralenes 44–45 desymmetrization, of oxetanes aromatization 1444 dendrimers, catalysts 1264 490 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1979

detection of intermediates 294 dialkyl peroxides, decomposition and diastereotopic deuterium oxide 489 840 atoms/groups 183 deuterium–hydrogen exchange dialkylamide bases see amides, and differential absorption 697 dialkyl 168 deuterium, and bond distance 26 dialkylcadmium reagent, with acyl and fractional distillation 168 and hydrogen bonding 112 halides 670 and fractional recrystallization and hydrogen exchange 629 dialkylcuprates 563 168 and proton 340 dialkylmagnesium 1132 and GC 168 and secondary isotope effects compounds, and Grignard and NMR 185 456 reagents 245 and nomenclature 160 exchange, arenium ions 612 dialkyloxiranes and hydrocarbons, and preparative LC 168 ions, and isotope effects 610 conversion to esters 1477 and resolution 167 isotope effects 304 dialkylperoxides 503 and the 2n rule 159 and dissociation energy 304 dialkylzinc compounds, and the and the E2 reaction 1274 labeling 440 Reformatsky reaction and X-ray crystallography 159 and the Shapiro reaction 1152 complexes 168 1309 diamagnetic ring current 55, 57 definition 158 in cationic rearrangements and aromaticity 71 epi and peri prefixes 159 1339 diamantine 1353 epimers 159 quadrupole echo spectroscopy diamides, by radical coupling of HPLC separation 175 123 amides 874 meso compounds 180 Dewar benzenes 1414 diamination, alkynes 1021 meso form 158 and [2+2]-cycloaddition 1063 metal catalysts 1021 nomenclature, erythro/threo and electrocyclic of alkenes 1021 160 rearrangements 1396 diamines, by reduction of azides nomenclature, “r” and “s” 159 and steric crowding 60 525 nomenclature, syn/anti 161 by photolysis of benzenes 1395 from addition of amines to physical properties 158 stability 1396 alkenes 1021 pseudoasymmetric carbon 159 structures 60 from aldehydes 1595 tartaric acid 158 Dewar formula 1063 from amides 1595 torsional 143 Dewar structures 33 from aziridines 525–526 diastereoselectivity, aldol and naphthalene 59 from bis(azides) 1021 condensation 1175 and resonance 49 from iminium salts 1595 and synthesis 162 dextro isomer 134 from oxime ethers 1596 conjugate addition 959 (DHQ)2PHAL, and oxidation to diene dinitriles Darzens condensation 1191 aminohydroxylation 1020 1472 Diels-Alder reactions 394 and asymmetric oxidative cleavage to diketones dihydroxylation 1009 dihydroxylation 1008 1464 Grignard reaction 1131 hydroamination 1021 diammoniumcalixarene 120 Knoevenagel reaction 1188 (DHQD)2PHAL, and asymmetric dianions, aggregates 370 Mannich reaction 1124 dihydroxylation 1008 alkylation 479, 578, 588 Michael addition 959 DHU 1231 carboxylic acids 588 and silyl enol ether 956 di-2-methoxyethyl dianions, diketones 1256 organolithium reagent reactions azodicarboxylate see diketones, mechanism 1256 1135 DMEAD diaryl carbenes 267 organometallic compounds, di-π-methane rearrangements diaryl ethers 492 conjugate addition 962 1432 diaryl selenides 510 reduction of ketones 1545 mechanism 1432 diaryl sulfides 508 sulfur ylids 1205 regioselectivity 1432 diaryliodonium salts 529 diastereotopic, and di(2-pyridyl)carbonate, and with sulfonamide salts 530 Cahn-Ingold-Prelog amides 1243 with thiophenols 784 system 186 diacetoxylation, of alkenes 1007, diarylthiiren-1,1-dioxides, thermal atoms 185 1009 decomposition to alkynes atoms/groups 183 DIAD 500, 517 1317 compounds, and NMR 185 diadamantyl compounds, barrier to diastereomers, and absolute definition 184 rotation 190 configuration 159 faces 185 diagonal hybridization 8 and Cahn-Ingold-Prelog rules diatomic molecules, and bond dialdehydes, by oxidative cleavage 160 energy 29 of epoxides 1464 and catenanes 130 energy curves 315–316 formation of cyclic alkenes and chiral recognition 169 diatropic 54 1597 and cis-trans isomers 175–178 annulenes 80, 82 dialkoxylation, of alkenes and diastereoselectivity 162 cyclooctatetraene dications 67 1008–1009 and diastereotopic 185 cyclopentadienide ion 64 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1980 SUBJECT INDEX

diaza(1,5)-bicyclo[3.4.0]non-5- from nitroso compounds 1329 diazonium group, leaving group, ene see DBN reaction with carbenes 273 in SRN1 reaction 779 diaza(1,8)bicyclo[5.4.0]undec-7- rhodium catalyzed diazonium ions 467, 638 ene see DBU decomposition 272 bridgehead 639 diazabicyclcooctane see DABCO with aldehydes or ketones diazonium salts 638, 762, 825 diazabicyclo[2.2.2]octane 182 1206 and aryl radicals 826 diazabicyclo[3.3.3]undecane 182 with enols 494 and carbenes 725 diazabicyclo[4.4.4]tetradecane with mineral acids 543 and carbocations 467, 1351 182 with oximes 494 and IUPAC mechanisms 467 diazabicyclo[7.3.1]tridecane 182 diazocarbonyl, insertion reactions and SN1 reactions 467 diazides 523, 531, 932 728 and superacids 467 diaziridines 139, 1208 diazoesters 715 and the Fischer indole synthesis thermolysis 271 and Stille coupling 717 1419 diazirines 1022 conversion to alkenes 1204 diazonium salts, arene, arylation and carbenes 271 insertion reactions 728, 1168 832 diazo compounds 825 via flow reactions 713 arylation, and radicals 832 alkylation 494 with engineered myoglobin arylation, mechanism 832 of carboxylic acids 502 1204 decomposition 826 and elimination 1310 diazoketones 502, 712, 726, 1363 with benzoic acid 832 and ultrasound 729 and Arndt-Eistert synthesis diazonium salts, aryl 532 by the Bamford Stevens 1363 and radicals 833 reaction 1310 and the Wolff rearrangement and SN1 mechanisms 829 conversion to anilines 1555 1364 conversion to aryl halides 827 from active methylene by diazo transfer reactions 713 conversion to aryl nitriles 828 compounds 712 conformations 1364–1365 dimerization 833 from alkyl amines 823 from acyl halides 1363 isolation of 467 from hydrazones 712, 1462 hydrolysis 485 methylation 829 from nitroso amides 1329 hydroxyl, conversion to alkenes photochemistry and eosin 832 from nitroso carbamates 1329 1322 reduction, reagents 1587 from nitroso ureas 1329 photolysis 1359 stability 823–824, 828 protonation of 467 and ring contraction 1364 with active methylene diazo compounds, with amines rearrangement to carboxylic compounds 710 521 acids 1363 with aromatic compounds 831 with boranes 593 ring contraction 1359 with boronic acids 801 with diselenides 508 with imines 1263 with copper halides 827 with imines, metal catalyzed with mineral acids 543 with CuCN 828 1167 diazomethane, alkylation of with organometallics 830 with ketones 1217 carboxylic acids 502 with oximes 830 with pyrroles 1081 and acyl halides 712 with sodium nitrate 829 with sulfene 1208 and Arndt-Eistert synthesis 712 with sulfur compounds 785 with sulfur 1208 and homologation of aldehydes with water 825 with thioketones 1208 to methyl ketones 1366 diazonium salts, conversion to diazo esters, and flow reactions decomposition to carbene 1073 cyclobutanes 1408 1071 flash photolysis 268 to sulfides 826 with ketones 1366 formation of carbenes 270 to sulfonyl halides 827 diazo-transfer reactions 712–713, photochemical decomposition to thiocyanates 826 1071 1073 to thiols 826 formation of diazoketones 713 photodecomposition 267 diazonium salts, coupling 610 versus azidination 713 photolysis 725 with aromatic compounds 638 diazoacetates, ethyl, with ketones reaction with CO 270 diazonium salts, cyclopropenium 1366 reagents for preparation 1329 467 with alkenes, metal catalyzed using flow reactions 1031 formation of radicals 840 1022 with alcohols 494 from aryl amines 824 with imines 1022 with aldehydes or ketones 1365 from diazoketones 485 diazoalkanes, and metal complex diazonium compounds, aromatic nucleophilic aromatic 1070 638 substitution, and SN1 771 base induced elimination of as leaving groups 466 reduction to amines 1565 nitroso compounds 1329 from amines and nitrous acid with sodium sulfite, cleavage to ethers 494 466 mechanism 1566 [3+2]-cycloaddition 1029, protonation of diazo reagents for 1587 1032 compounds 467 SN1 reaction 771 decomposition to carbenes 270 diazonium group, as a leaving solid 638 decomposition to ketenes 1262 group 823 Sonogashira coupling 818 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1981

stability of 467 dicarboxylic acids, and hydrogen dicyclohexylurea, from Stephens–Castro coupling 818 bonding 107 DMSO-DCC oxidation tetramethyltin catalyzed and statistical effects 366 1451 methylation 830 bis(decarboxylation) to alkenes didehydroannulene 86 with carbon monoxide 830 1475 Dieckmann condensation 1253 with sulfur 1208 bis(decarboxylation), See also Claisen diazotization 825, 1588 mechanism 1475 condensation and flow chemistry 337 by cleavage of cyclic ketones and the acyloin condensation of amines 467, 1339 1465 1599 of amino acids 543 cleavage to ketones 1475 catalyst for 1255 of aniline derivatives, conversion to cyclic ketones mechanism 1255 mechanism 823 1257 microwaves 1254 with metal halides 543 decarboxylation versus solvent free 1254 Dibal-H see Dibal anhydride formation dielectric constant, and solvent Dibal, and ammonium chloride 1236 acidity 353 601 dehydration 1236 dielectric heating, and microwaves functional group reactivity from cyclic ketones, reagents 334 1533 for 1465 dielectric screening effects, metal mediated reduction of oxidative cleavage of cyclic algorithm 469 alkenes 1522 alkenes 1470 in solvents 469 reduction of aldehydes and with alcohols 1228 Diels-Alder reactions 311, 898, ketones 1533 dicarboxylic esters, oxidative by 1035–1055, 1057, 1081 reduction of esters to aldehydes cleavage of 1,3-diketones Diels-Alder reactions, 1551 1466 acceleration, high pressure dibenzo[fg, op]tetracene, dications 229 1038 conversion to quaterphenyl alkane 233 hydrogen-bonding 1038 1398 as a guest 121 hydrophobic effect 1038 dibenzo[g, p]chrysene, from cyclobutyl 72 in water 1038 bifluorenylidene 1399 dichloroboranes 933 ionic liquids 1038 dibenzoannulene 83 dichlorine monoxide 863 micellular effects 1038 dibenzodihydropentalenofuran dichloro (2,3)-5,6-dicyano-1,4- microwave irradiation 1038 329 benzoquinone see DDQ phosphate 1039 dibenzosemibullvalenes 329 dichlorocarbenes 266, 268 solid state 1038 thermal isomerization 329 dichloroketones 707 ultracentrifuge 1038 diborane 932 dichloromethylene 266 ultrasound 1038 diboration, and dihydroxylation carbene 269 zeolites 1038 1009 dichloromethylsilane, with Diels-Alder reactions, allenes diboron carbenes 268 alkynes 941 1053 diboronic acid, and aryl halides dichotomy, syn/anti, and Diels-Alder reactions, and 738 elimination 1278 [3+2]-cycloaddition see dibromides, benzylic 863 dichroic behavior 143 [3+2]-cycloaddition gem-, from aldehydes and dichromate, oxidation of alcohols Diels-Alder reactions, and bromine-triphenyl 1447 azadienes 1054 phosphite 1127 oxidation of hydroquinone and azadienes, ultrasound dibromoalkenes, with alkynyl 1459 1054 carboxylates 945 pyridinium see PDC and azo compounds 1053 dibromo (1,3-)-5,5- dicobalt octacarbonyl, and and benzyne intermediates dimethylhydantoin carbonylation of aryl 295 863 halides 821 and benzynes 1041 dibromo-5,5-dimethylhydantoins, hydroformylation 990 and chiral auxiliaries 1040 aryl halides, halide and hydroformylation 990 and diene conformation 1039 exchange 792 formation of ketones 742 and exo addition 1040 dibromoborane 935 with organometallics 742 and flow reactions 1038 dibromoethane, and dipole Dictionary of Organic and high pressure 1041 moment 20 Compounds 1630, 1632 and hydrophobic acceleration conformations 190 Dictionary of Organometallic 391 dibromoketones 707 Compounds 1620 and ionic liquids 394, 1037 dibromomethane, and carbenoids dicyclohexano-18-crown-6 476 and lactim ethers 1054 1074 dicyclohexyl urea, and Moffatt and microwave chemistry 334 bond angles 27 oxidation 1451 and retro-Diels Alder 1324 DiBuIm, ionic liquids 394 dicyclohexylcarbodiimide see and sonochemistry 333 dicarborane, reduction of aryl nitro DCC and substituent electronic compounds 1600 dicyclohexylurea see DHU effects 1036 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1982 SUBJECT INDEX

Diels-Alder reactions, and nitroso 1053, 1055 by thermal extrusion of carbon azadienes (Continued) normal 1050 dioxide from lactones and TEMPO 1054 of cyclobutadiene 73 1324 and the Claisen rearrangement organocatalysts 1037 carboalkylation, intramolecular 1415 Diels-Alder reactions, orbital 948 Diels-Alder reactions, antarafacial, overlap 1051 carbonylation 984 bond formation 1050 polar 1044 catalytic hydrogenation 1516 antarafacial, HOMO-LUMO proximity-induced 1037 cisoid and transoid 1051 radical cation catalysts 1038 conformations 1036 antibody catalysts 1037 radical mechanism 1044 conformations, and reactivity aqueous, catalysts 1037 rate acceleration 1038 1036 aza- see aza-Diels-Alder rate of reaction 1044 conjugate systems 898 azadienes 1053 rearrangements 1039 conjugated 720 biradical mechanism 1045 regioselectivity 1040 and carbocations 228 Brønsted-Lowry acid ionic retro- 1043, 1047 and electrophilic addition liquids 1037 reversible 1043 904 catalysts 1037 secondary orbital interactions carbomagnesiation 947 cationic catalysts 1038 1040 hydration 914 chemoselectivity 1037 secondary overlap of orbitals hydroboration 936 compatible functional groups 1051 with carbenes 1070 1036 selectivity 1039 conversion to bicyclobutanes concerted 1045 singlet oxygen 1056 1431 dehydrogenative 1043 solvent effects 1038 to cyclic alcohols 1385–1386 diastereoselectivity 394 stereochemistry 1039 dienes, cyclic, from monocyclic diene conformation 1036 suprafacial bond formation alkenes 1430 diion mechanism 1044 1050 lactone formation 1026 disrotatory motion 1039 symmetry considerations photochemical ring opening to enamides and alkynes 1054 1051 trienes 1389 enantioselective 1040 twisted 1050 thermal extrusion of carbon endo addition 1040 with aldehydes 1053 monoxide 1324 formation of cyclohexadienes with arynes 774 dienes, cyclization 944 1041 Woodward-Hoffmann rules preparation of bicyclic alkenes frontier orbital method 1045 1045 943 furans 1055 Diels-Alderase enzymes 1037 dienes, cycloaddition of oxygen heteroatom 1051–1055 diene dinitriles, from diamines 1055 hexahydro-, cycloisomerization 1472 of singlet oxygen 1056 1043 dienes-cyclobutene with alkenes 1035–1055 homo 1042 interconversion, orbital dienes, dimerization in the Kolbe Diels-Alder reactions, HOMO and requirements 1392 reaction 885 LUMO interactions dienes-cyclobutene, disrotatory transition state 1393 1044–1045, 1052 interconversion, with epoxidation 1015 imines 1053 aromatic rings 1395 extrusion of carbon monoxide in aqueous detergent solutions dienes, acylation 720 1324 391 addition of alkanes 940 from alkene-halo sulfones 1317 in water 391 alkylation 578 from alkenyl boranes 1388 intramolecular 214, 1042 and cis/trans nomenclature 177 from alkenylzinc compounds organocatalytic 1042 dienes, and E/Z nomenclature 177 560 tether length 1043 and homoconjugation 45 from alkynes 949 inverse electron demand 1045 and photochemistry 317 from alkynyl alcohols 1300 ionic, catalysts 1037 and radical cyclization 897 from bicyclobutanes 1431 isomerization of allenamides and radicals 897 from conjugated esters 1202 1054 and ring closing, orbital overlap from cyclic amines 1306 lithium perchlorate in ether 1392 from cyclobutenes 1389–1391 1039 and s-cis conformation 1400 from 1,5-dienes 1408 lithium triflate in acetonitrile and symmetry of orbitals 1391 from dienes and alkenes 945 1039 and the Prins reaction 1214 from organocuprates 556 mechanism 1043 and UV 317 from organometallics and allylic electrophilicity– dienes, antarafacial migration halides 559 nucleophilicity indices 1401 and vinyl halides 559 1044 bicyclic, and strain 217 from propargylic ethers 1301 Mobius-H¨ uckel¨ method 1045 by based induced elimination of from propargylic systems 909 N-heterocyclic carbene halo sulfones 1317 from thiophene-1,1-dioxides catalysts 1037 by cheletropic reactions 1317 1317 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1983

from vinyl sulfones and allenes diesters, as a guest 123 with lithium 1135 942 diethyl azodicarboxylate see with organolithium reagents from vinylboranes, NaOH, and DEAD 1135 iodine 1388 diethyl tartrate, and epoxidation conversion to dithioacetals 509 functionalized 1052 1017 from amines 1492 dienes, HOMO and LUMO 1044, (diethylamino)difluorosulfonium dihalides, hydrolysis of 484 1393 tetrafluoroborate see vinyl 997 Huckel¨ system 1393 XtalFluor-E dihaloamines 763 hybridization 41 diethylaminosulfur trifluoride see dihalocarbenes 272 hydroamination 928 DAST and insertion reactions 272 intramolecular metathesis 1430 diethylene glycol 497 dihalocyclopropanes 1070 metal catalyzed coupling of and Huang-Minlon dihalogenation, of ketones 706 Grignard reagents 881 modification 1577 dihedral angles see angle nonconjugated, from vinyl and Wolff-Kishner reduction dihedral angles, and halides with dienes 942 1577 anti-elimination 1277 organometallic reagents, and diethylmagnesium 246 and conformation 193 carbon dioxide 988 diethylmercury 248 dihydrobenzopyrans, by photochemical ring closure to diethylzinc, and organocopper Diels-Alder reaction 1054 cyclobutenes 1389 reagents 558 dihydrocinchonidine, chiral photochemistry 1432 and Simmons-Smith reaction, additive 493 photooxidation 1055 mechanism 1075 dihydrofurans 919 polymer supported 1053 differential absorption, and dihydroindoles 788 radical addition, and the diastereomers 168 dihydroisoquinolines, Felkin-Anh model 899 and resolution 169 Bischler-Napieralski reaction with ketones 1053 differential hydration, and amines reaction 655 reaction with radicals 897 371 dihydropyrans, from Grignard reactivity in Diels-Alder 1036 and basicity 371 reagents 570 1,5-dienes, and Cope differential solubility 166 from vinyl oxetanes 1408 rearrangement 1409 diffusion control, proton-transfer dihydrothiepin-1-1-dioxides, rearrangement 1409 reactions 350 thermal elimination to dienes, ring closure, conrotatory diffusion rate, and reactivity 390 trienes 1317 motion 1394 diffusion-controlled reactions 285 dihydroquinidines, and conrotatory versus disrotatory diffusion-ordered NMR asymmetric 1394 spectroscopy see DOSY dihydroxylation 1008 disrotatory motion 1394 difluoro, gem-compounds, dihydroquinines, and asymmetric dienes, s-cis and s-trans reagents 1128 dihydroxylation 1008 formations 1036 difluorocarbene, and flow dihydroxylation, and alkene sigmatropic migration of reactions 1069 structure 1009 hydrogen 1400 difluorohomologation 1366 and chiral ligands 1008 Simmons-Smith reaction 1075 of ketones 1366 and Cinchona alkaloids 1008 suprafacial migration 1401 dihalides, and aldol condensation and diboration 1009 thermal opening of 484 and hypervalent iodine 1008 cyclobutenes 1389 and the Cannizzaro reaction and ionic liquids 1008 thermodynamic stability and 484 and microwaves 336 Cope rearrangement 1409 conversion to aldehydes or and organocatalyst 1007 via 1,4-elimination 1319 ketones 484 and osmium complex 1006 via organometallic coupling conversion to allenes 1319 and phase transfer reagents 559 conversion to cumulenes 1319 1006 via Stille coupling 717 dehalogenation 1319 and phthalazines 1009 with diketones 950 with metal catalysts 1319 and potassium ferricyanide with HBr 898 formation of Grignard reagents 1009 with imines 1054 747 and Pseudomonas putida 1010 with quinones 1036 from alkynes 911 and steric hindrance 1009 with radicals 899, 912 from halogenation of alkenes dihydroxylation, anti 1006 dienone–phenol rearrangement 992 neighboring group mechanisms 1360–1361 dihalides, gem-, from aldehydes 1007 arenium ions 1360 and metal halides 1127 dihydroxylation, asymmetric mechanism 1360 from aldehydes or ketones 1008 dienophiles, azo compounds 1053 1127 and (DHQ)2PHAL 1008 definition 1035 mechanism 1128 and (DHQD)2PHAL 1008 iminium ions 1053 SN1 process 1128 and AD-mix-α 1009 in the ene reaction 952 from Grignard reagents, and and AD-mix-β 1009 dienynes, photocyclization 1392 elimination 747 and phthalazines 1008 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1984 SUBJECT INDEX

dihydroxylation, diisopropylamide, lithium see of vinylboranes 883 diastereoselective 1009 LDA of ylids 1201 enantioselective 1008–1009 diisopropylethylamine see dimethoxyethane see DME in ionic liquids 394 Hunig’s¨ base dimethylacetamide see DMA lipase catalyzed 1007 1,3-diketones, with diazomethane dimethylbenzylamine see DMBA of alkenes 1005 1366 dimethyl dioxirane see dioxirane, and kinetic resolution 171 1,4-diketones 979 dimethyl catalysts for 1006 diketones, acid catalysis 1103 dimethylenecyclobutenes, from enantioselectivity 1008 acid catalyzed formation of diynes 1410 in ionic liquids 1006 furans or pyrans 1103 dimethylenecycohexane-1,4-diyl regioselectivity 1008 acidity 368 radical 261 syn addition 1005 autoxidation 1466 dimethylformamide dimethyl dihydroxylation, of alkynes 1007 diketones, by oxidation of alkynes acetal, and elimination of of aromatic compounds 1010 1501 hydroxy acids 1323 enzymatic 1010 of alkynes, metal catalysts dimethyl-2-imidazolidinone, Escherichia coli JM109 1501 solvent 1164 (pDTG601) 1010 reagents 1501 dimethyl(methylthio)sulfonium dihydroxylation, of vinyl ethers of cyclic alkenes 1500 salts, and amines 1025 1007 diketones, by oxidative cleavage of dimethyloxosulfonium methylid phthalazines 1008 diamines 1464 1204, 1207 Prevost reaction 1006 by oxidative coupling of enolate and resonance 1205 Sharpless asymmetric 1008 anions 1509 dimethyl sulfide see sulfide syn 1006 by oxidative coupling of silyl dimethyl sulfoxide see DMSO ultrasound 1006 enol ethers 1509 dimethylsulfonium methylid Woodward modification of the by rearrangement of epoxy 1204 Prevost reaction 1007 ketones 1356 and resonance 1205 diimides, and hydrogenolysis of by α-oxidation of ketones dimethyltitanocene see Petasis amines 1584 1487 reagent from hydrazine 1521 diketones, cleavage by base 757 dimethylzinc, homocoupling 562 from hydroxylamine 1521 with Oxone 1465 dimolybdenum tetraacetate, and intermediates, in McFadyen diketones, dianions 1256 circular dichroism 155 Stevens reduction 1552 mechanism 1256 and enantiomers 155 intermediates, in reduction diketones, from acyl halide dinitriles, and the Thorpe reaction 1552 conjugate addition 979 1209 reduction of alkene, mechanism acyl halides 1252 formation of imidines 1126 1521 from alkynes, reagents 1501 from conjugated dinitriles 913 reduction of alkenes 1521 from aryl carboxylic acids 1599 reduction with SmI2 1584 reduction of nitro compounds from cyanohydrins 980 Thorpe-Ziegler reaction 1209 1566 from ketones and esters 1255 2,4-dinitroanilinium ion, indicator stability 1521 α-oxidation of ketones, for pK 352 with alkenes 1521 reagents, for 1487 dinitromethane, carbanion 240 diiodomethane, and carbenoids diketones, oxidative cleavage of dioic acids, from cyclic diketones 1074–1075 cyclic alkenes 1470 1466 diioinic intermediates, pKa 363 diols, acid catalyzed [3+2]-cycloaddition 1031 rearrangement to hydroxy acids rearrangement to ketones diions, intermediate 1065, 1067 1361 1354 and the Cannizzaro reactions superoxide 1466 and formation of cyclic sulfates 1602 unsymmetrical 1252 482 mechanism, with alkenes 950 by Gomberg-Bachmann pinacol [2+2]-cycloaddition with hydrazines 1117 synthesis 1593 reactions 1065–1066 with ortho esters 1103 by pinacol coupling 1594 mechanism, Diels-Alder dilithiated carboxylic acids 734 by the Prins reaction 1213 reaction 1044 dilongifolylborane 935 by Tollens’ reaction 1193 diisobutylaluminum hydride see dimer mechanism, and SNAr carbocations, and Dibal reactions 770 rearrangements 1341 dihydrothiophene-1-1-dioxides, dimeric benzene 113 cleavage 1322 thermal elimination to dimeric borane 933 by led tetraacetate, cyclic dienes 1317 dimerization, of alkenes 942 transition state 1464 diisopinocampheylborane 171, of aryldiazonium salts 833 with lead tetraacetate, 935 of carbenes 273, 727 mechanism 1464 with alkenes 934 of ketenes 1261 and chiral lead carboxylates diisopropyl azodicarboxylate see of nitrenes 277 1464 DIAD of radicals 254 diols, conversion to alkenes 1316 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1985

1,2-diols, conversion to epoxides dipalladium catalysts 988 and pyrazoles 1330 493 dipamp, and catalytic and rearrangements 1347 diols, conversion to ketones 1354 hydrogenation 1515 and resonance 47 cyclodehydration 500 dipeptides, catalyst, for and singlet oxygen 870 dehydration 1300 epoxidation 1013 and spin conservation 1062 deoxygenation 1315–1316 diphenyl diselenide 716 and spin inversion 1062 to give alkenes 1315 for preparation of arylselenides and tritium labeling, dihydroxylation of alkenes 785 rearrangements 1348 1005 diphenylmethyl carbanions 239 biphenylene pyrolysis 1399 from aldehydes 1594 diphenylmethyl carbocations 228 intermediate, from alkenes 1006 diphenylphosphide, lithium, [2+2]-cycloaddition from epoxides 489, 1006 cleavage of ethers 520 reactions 1066 and peroxyacids 1434 diphenylpicrylhydrazyl radical intermediates 1358 from ketones 1594 256, 299 lifetime 261 in situ generation, and oxidative diphosphacrowns 118 mechanism 1059, 1411–1412 cleavage 1463 diphosphanes 183 Diels-Alder reaction 1045 mechanism of formation, and diphosphines see bis(phosphines) photochemical SN2 1007 diphosphorus tetraiodide 1238 [2+2]-cycloaddition 1060 oxidation 1006, 1457 dipleiadiene, paratropic 87 oxygen 867 lactones 1494 dipolar addition see cycloaddition directed aldol condensation 1178 to lactones, reagents 1494 [1,3]-dipolar addition 1027–1035 directed metalations 732 diols, oxidative cleavage 1463 See also addition directed ortho metalation 552, enantioselectivity 1463–1464 dipolar addition, and FMO 1029 806 mechanism 1464 dipolar compounds, table 1029 directionality, approach of reagents for 1463 dipole induced bonding 119 nucleophiles to carbonyls with lead tetraacetate 1463 dipole moment 19 1092 with periodic acid 1463 and C—H 20 dirhodium catalyzed insertion diols, rearrangement 1354 and conformation 190 726 reductive coupling of aldehydes and Debyes 20 dirohodium catalysts, and carbene or ketones, reagents 1593 and ionization reactions 892 insertion 726 with acids 1354 and symmetry 20 diselenides 716 with periodic acid, mechanism azulene 68 and radicals 863 1464 canonical forms 1,3- 1028 catalytic hydrogenation 884 with thiophosgene 1316 induced 17, 20 reduction to selenols 1593 with tosic acid 504 MO calculations 37 with alkenes 1018 1,4-diones, photolysis 1333 of substituted aromatics 20 with aziridines 575 dioxanes, and conformations 200 parallel, and anomeric effect with diazo compounds 508 and oxonium ions 419 201 disiamylborane 934 and solvolysis 419 1,3, structural types and table with alkenes 934 twist conformation 201 1028–1029 disilanes, with aryl halides 822 dioxaspiro 1061 diprotic acids, statistical effects dispalure 998 dioxetanes, cleavage 1056 and acidity 366 displacement mechanism, and cycloaddition of singlet oxygen dipyridiniumditribromide (1,2-) oxidation–reduction 1441 to alkenes 1056 ethane, brominating agent disproportionation, and aryl intermediate 1056 537 radicals 846 dioxiranes, and peroxyimidic acid dipyrrinones, and hydrogen and dehydration of carboxylic 1013 bonding 112 acids 1236 and strain 208 diradicals 260–261, 327 See also and radicals 263 chiral 1014 biradicals and the benzidine dioxiranes, dimethyl 1013 and Bergman cyclization 1395 rearrangement 1423 as oxidation reagent 1455, and Criegee mechanism of aryl carboxylate ions 684 1459, 1462, 1478, 1483, ozonolysis 1467 of aldehydes 1601 1484, 1502 and [3+2]-cycloaddition 1034 of carbenes, mechanism 727 oxidation of isocyanates to nitro and cyclopropane ring opening disrotatory motion, and compounds 1503 1358 electrocyclic of thiols 1505 and di-π-methane rearrangements 1390 oxidative cleavage of diamines rearrangements 1432 Diels-Alder reactions, 1464 and DNP 254 selectivity 1039 dioxiranes, oxidation of and extrusion of nitrogen 1330 dissociation energy, and bond isocyanates 1503 and Norrish Type II cleavage energy 29 ozonolysis intermediate 1470 327 and deuterium isotope effects dioxolanes from diethylacetals and Paterno-Buchi¨ reaction 304 496 1060 radicals, table 258–259 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1986 SUBJECT INDEX

dissociation, radicals, and dithiocarbamates, from carbon DMBA, and absolute photo-Fries rearrangement disulfide, amines and configuration 155 676 boronic acids 1105 DME (1,2-dimethoxyethane) 247 dissociation, spontaneous 896 dithiocarbamic acid salts, carbon and organolithium reagents 247 dissociative states 319 disulfide and amines 1126 solvent 1188 and photolytic cleavage 320 dithiocarboxylic acids, DMEAD 500 dissolving metals, cleavage of organometallics with CO2 DMF, and the Gabriel synthesis ethers 540 1162 530 reduction of alkyl halides dithiocarboxylic esters 1232 with acyl halides 1239 1568 and potassium thioacetate 501 with dihaloalkenes 720 reductions 1524 dithioesters, conversion to esters DMSO (dimethyl sulfoxide), and distance, bond see bond distance 1233 DCC, oxidation of distance, bond 26 dithioketals, aldehyde or ketone alcohols 1451 distillation, fractional, and protecting group 1108 and Moffatt oxidation 1451 diastereomers 168 by alkylation 588 and oxidation of alkyl halides to and resolution 168 Corey-Seebach procedure 1108 aldehydes 1490 distorted aromatics 50 desulfurization with Raney and pKa 344 disulfides 511 nickel 1110 and Swern oxidation 1451 and Smiles rearrangement 838 hydrolysis, Core-Seebach oxidation of alkyl halides, and sulfurization 1109 procedure 1110 mechanism 1490 aryl, from aryl halides 785 protecting group 1108 reagents utilized for oxidation with alkenes, and metal salts reagents for 1108 of alcohols 1451 1018 for hydrolysis 1110 reagents, and oxidation of disulfides, by oxidation of thiols dithiolanes, desulfurization 1589 alcohols 1451 1505, 1510 dithiols, from carbonyls 1107 variations in oxidation reagents mechanism 1510 ditosylamines, leaving group 501 1451 reagents 1509–1510 ditosylate, leaving groups 466 with acetic anhydride 1603 reversible 1510 divinyl ether, and cross with silyl halides and alkenes disulfides, from alkyl halides 510 conjugation 44 1000 Bunte salts 510 divinyl oxiranes, Cope DNA, and molecular knots 131 from sulfonic acids 1590 rearrangement 1410 DNP (dynamic nuclear from thiobenzoates 1590 divinylcyclobutanes, polarization), and NMR from thiols 1509 rearrangement 1410 254 halo, with base 999 divinylcyclopropanes, and biradicals 254 ions, with alkyl halides 510 rearrangement 1410 dodecahedral carbocations 234 reduction to thiols, reagents diynes, alkene metathesis 1430 dodecahedrane 1447 1593 alkynes, trimerization 1077 and dehydrogenation 1446 with alkenes 1018 and hyperconjugation 42 Doebner modification, and with enolate anions 716 and metathesis 1430 microwaves 1188 dithianes 1108 and the Eglinton reaction 876 of the Knoevenagel reaction acidity 1110 and the Hay reaction 876 1188 acylation 1256 by Cadiot-Chodkeiwicz domino metathesis 1429 alkylation 588, 1110 reaction 877 domino reactions 1187 and conformations 200 by Glaser reaction 877 donor–acceptor complexes, and the Brook rearrangement by the Hay reaction 877 electron 114 1110, 1438 conjugated 41 DOSY, and π−π interactions 113 and Umpolung 589, 1110 conversion to Dotz¨ benzannulation, and Alkynes desulfurization 1589 dimethylenecyclobutenes 1079 from aldehydes 588 1410 and Fischer carbene complexes from carbon disulfide, NaBH4, 1,5-Cope rearrangement 1410 1079 and dihalides 509 cyclization, metal catalyzed double alkylation 576 hydrolysis 589 943 double asymmetric synthesis 165, with epoxides 1438 from alkyl–alkynylborates 884 1177 with organolithium reagents from alkynes 877 double Baylis-Hillman reaction 588, 1438 hydrothiolation 923 1166 dithioacetals, alkylation 588 metal catalyzed coupling of double bonds, and bond energy 32 catalytic hydrogenation 884 alkynes 875 and delocalization 39 Corey-Seebach procedure 1108 coupling of Grignard conjugated with p orbitals 42 from gem-dihalides 509 reagents 881 cumulative 144 protecting group 1108 transfer hydrogenation 1520 from carbocations 236 reagents for 1108 DMA, and carbonylative cross in conjugation with for hydrolysis 1110 coupling 561 carbocations 228 reduction 1588 DMBA 155 isomerization 698–699 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1987

rearrangements 699 and Hofmann elimination 1306 SRN1 reactions 775 strain 220 IUPAC mechanism 1274 electrocyclic reactions, and α,β-versusβ,γ-preference 909 E2 reaction see elimination formation of aromatic double carbonylation 605 and bond rotation 1278 compounds 1398 double hyperconjugation 227 rate determining step 1274 and Mobius-H¨ uckel¨ method double metathesis 1429 E2 versus SN2 1281 1391 double Michael addition 977 E2, and alkyl halides 1311 ene-diynes 1395 double Pauson-Khand reaction bond angles 1277 electrocyclic rearrangements 986 isotope labeling 1277 1389 double-asymmetric synthesis 935 planar transition state 1277 allowed versus forbidden 1396 double-twist Mobius¨ aromaticity and rotamers 1278, 1291 and Dewar benzenes 1396 1049 and vinylogy 1277 and orbital symmetry 1396 doubly interlocking catenanes 130 concerted loos of proton and and overlap of HOMO orbitals downfield shift 55, 57 halide 1285 1391 Doyle catalyst 308 in cyclic alkyl halides 1277 conrotatory versus disrotatory dry ice see carbon dioxide isotope effect 1277 1390, 1396 dry media reactions 395 stereochemistry 1291 definition 1391 dry-reaction microwave chemistry stereospecificity 1274 forbidden, and metal catalysts 334–335 transition state 1291 1396 drying agents, and acetal or ketal eclipsed conformations 189 frontier orbital method 1391 formation 1101 eclipsing bonds, and conformation metal catalyzed 1396 and imine/enamine formation 192 stereochemistry 1390 1113 eclipsing conformation 194 4n versus 4n+2 1396 dual substituent parameter ECRE see extra-cyclic resonance electrocyclic ring opening, and equation 386 energy UV light 1389 Duff reaction, and aryl aldehydes EDA complexes 114, 691, 1063 benzocyclobutenes 1389 666 %ee see enantiomeric excess conrotatory versus disrotatory mechanism 667 eEROS 1626 1391 dyes, azo, by diazonium coupling α-effects, and nucleophilicity 463 cyclic dienes 1389 638 Eglinton reaction 876 cyclobutenes 1389 dynamic kinetic resolution 581 mechanism 877 substituent effects 1389 dynamic NMR 203 scope 876 torquoselectivity 1390 dynamic nuclear polarization see Ehrlich-Sachs reaction 1169 electrocyclization, ketene-iminium DNP Ei reactions See also elimination salts 1392 dyotropic rearrangements 1436 Ei reactions, Chugaev reaction electrofugal activity, carbon and σ-bond migration 1437 1305, 1307 dioxide 684 Brook rearrangements 1437 decarboxylation of esters 1304 electrofuge 411 lactones 1437 dehydrohalogenation 1313 and E2 reactions 1274 mechanism 1297 definition 280 E/Z nomenclature, definition Elbs reaction 674 alkenes from epoxides 1302 176 elections, unpaired, and ESR 253 and carbonylation of amines E1 mechanisms 1280–1281 electric field, and microwaves 334 765 and Grob fragmentation 1322 electrical effects, and reactivity and Collman’s reagent 602 E1 reactions, kinetics 1281 375 and halogenation of carboxylic conjugate base effects 1281 electrochemical, halides, acids 709 E1-E2-E1cB Spectrum 1286 elimination to alkenes and hydroxylation 1484 and volume of activation 1287 1318 and phenol formation 674 isotope effects 1287 electrochemistry, amides to esters and the Hofmann Spectrum, tunneling 1287 1235 rearrangement 1370 E1anion, mechanism 1283 amination 873 aryl fluorides 1570 E1cB mechanism 1281 and the haloform reaction 758 formation of haloalkynes 740 alkenes from halo ethers 1321 and the Michael addition 956 of carboxylate salts 885 and ion pairs 1285 and the Prins reaction 1215 sulfoxide reduction 577 isotope effects 1284 and Ullmann reaction 798 electrolytic halogenation, with leaving groups 1283 carbonylation of alkyl halides Nal 708 nucleofugal ability 1284 603 electrolytic methods, formation of rate determining step 1283 coupling of silanes 875 radicals 263 solvent effects 1282, 1284 formation of carbenes 270 electromagnetic spectrum 315 E1cB reactions see elimination oxidation of alcohols 1456, electromagnetic waves, and (E1cB)I mechanism 1285 1458 microwaves 334 E2 and electrofuges 1274 of thiols to disulfides 1509 electromotive series, and E2 mechanism 893 reduction of aryl nitro transmetalation 744 and Grob fragmentation 1322 compounds 1600 metals 744 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1988 SUBJECT INDEX

electron affinity, and and electron affinity 17 hydrogen 629 electronegativity 17 and electron cloud distortion 17 with carbanions 249 and organolithium reagents 247 and electron density 19 electrophilic addition 281, 892 electron cloud distortion, and and I effects 21 See also addition electronegativity 17 and ionic bonds 19 with allenes 904 electron configuration 8 and ionization potential 17 with conjugated dienes 904 of boron 8 and NMR 19 electrophilic aromatic substitution of carbon 9 and resonance 48 see substitution electron delocalization, and enol and valence shell electrons 18 electrophilic aromatic substitution, stabilization 701 formula 17 HSAB 625 of amides 98 group electronegativities 19 multiple substituents 621 electron density, and cyclopropane of C and H 20 resonance between groups 625 208 of groups 18 scale of reactivity 626 and electronegativity 19 scales 18 selectivity relationship 626 and neighboring groups 428 table 18 electrophilic carbenes 1068 and nodes 5 electronic configuration, boron 8 electrophilic halogenation 857 and resonance 48 electronic effects, alkene addition electrophilic mechanism 861, 913 map, acetylene 12 905 halogenation of alkenes 993 potential map, aniline 48 and basicity 366 electrophilic radicals 845, 902 electron diffraction, allyl radical and the Diels-Alder reaction electrophilic reactions 280 254 1036 electrophilic rearrangements 282, and bond distance 24 electronic excitation 316 1335, 1349 and conformations 188 electronic spectrum 316 electrophilic substitution see electron donating groups 21 electronic structure 15 substitution and the tetrahedral mechanism and electrons 15 electrophilic substitution reactions 455 boron trifluoride 17 829 and σ-values 382 covalent compounds 16 electrophilicity–nucleophilicity substituent effects 454 imines 17 indices, Diels-Alder electron donor–acceptor methane radical 17 reaction, mechanism 1044 complexes 114 of ethylene 16 electrophilicity, and carbocations electron paramagnetic resonance of mercury 8 410 see EPR of nitrogen 13 and SN1 reactions 410 electron potential map, of oxygen 16 index 411 benzenonium ion 611 of PCl5 and SF6 16 of carbenes 1068 ethylene 10 P and S compounds 16 electroreduction, formation of pyrrole 62 sulfuric acid 17 amino alcohols 1596 electron promotion 8 electronic transfer, electroreduction, oxime ethers electron repulsion, and oxidation–reduction 1441 1596 nucleophilic strength 463 electronic transitions, and electrostatic effects 113 electron spin 5 photochemistry 314, 316 electrostatic potential map, electron spin resonance see ESR electrons, and annulenes 71 benzene 34 18-electron systems, and and electronic structures 15 butadiene 40 metallocenes 67 and ESR 252 electrostatic scale, resonance electron transfer, and and radicals 250 effects 38 photosensitization 325 and resonance 46 electrosynthesis 1106 radicals 840 as waves 3 element effect, and leaving groups electron withdrawing groups 21 bonding 33 446 and bond energy 32 lone pair, and carbanions and SNAr mechanism 769 and the tetrahedral mechanism stability 241 α-elimination reactions 1273 532 lone pairs 28 β-elimination reactions 281, 1273 and vinylic substitution 447 nonbonded, and carbenes 266 1,3-elimination reactions 1322 and σ values 382 overlap 5 Grob fragmentation 1322 substituent effects 454 promotion 9 halo amines 1322 electron, delocalization 96 solvated 775 1,4-elimination reactions 1317 electronegativity 17 steric requirements 28 formation of cumulenes 1319 electronegativity scale, Pauling 18 unpaired, and radicals 251 formation of dienes 1319 Sanderson 18 valence 15–16 1,6-elimination reactions 1317 electronegativity, and acidity 365 valence shell, and elimination reactions, aldehydes, and basicity 365 electronegativity 18 with organometallics 1136 bond energy 17, 30 electrophilic mechanism 919 elimination reactions, and and chemical shift 19 electrophile, and Lewis acids 607 branching, table 1293 and E/Z inversion barrier for definition 280 and Bredt’s rule 1288 radicals 256 Friedel-Crafts alkylation 651 and Brønsted equation 1288 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1989

and carbenes 274 and syn-periplanar E1 versus E2 versus E1cB and carbenoids 271 conformations 1276 1295 and DBN and DBU 1311 and Zaitsev’s rule 1276 stereochemistry 1290, 1296 and decarbonylation of anti-elimination 1275 steroids 1296 aldehydes 889 axial versus equatorial leaving substrate reactivity 1291 and dehydration of alcohols groups 1278 substrates, structure 1291 495 in cyclohexyl halides 1278 E1 versus E2 versus E1cB 1292 and diazo compounds 1310 mechanism 1273–1274 E1 versus SN1 1292 and entropy of activation 333 ab into study 1274 elimination reactions, sulfoxides and extrusion reactions 1273 stereospecificity 1274 1297 See also sulfoxides and formation of nitrenes 276 steric effects 1280 syn 1277 and HMPA 1312 transition states 1287 and ammonium salts 1278 and Hofmann’s elimination versus SN2 1292 and ion-pairing 1279 1290 E2, with alkyl halides 1274 solvent effects 1279 and Hofmann’s orientation elimination reactions, E2C, transition states 1287 1290 mechanism 1287 syn/anti dichotomy 1278 and Hofmann’s rule 1289, 1292 effect of the base 1293 temperature effects 1295 and hyperconjugation 1289 effect of the leaving group 1294 to form alkynes 1276 and ionic liquids 1312 elimination reactions, Ei and transition state 1286–1287 and LDA 1312 pyrolysis of sulfoxides types 1273 and substitution 1292 1311 versus substitution 1281 elimination reactions, anti- and ion and Chugaev reaction 1305 leaving groups 1293 pairing 1280 and Cope elimination 1307 solvent effects 1295 anti-elimination 1275 and Hofmann elimination 1306 xanthates 1297 aza-Cope 1308 mechanism, decarboxylation of elimination–addition reactions, base induced 1293 esters 1304 mechanism see of ethers, mechanism 1301 elimination reactions, entropy of mechanism of sulfones 1310 activation 1296 elimination–addition reactions, carbocation transition state fragmentations 1321 and Mannich bases 449 1297 Grignard reagents, dihalides and sulfones 449 conjugate 1298 747 of Mannich bases 466 elimination reactions, Cope see elimination reactions, Hofmann emission of light, and Cope see Hofmann elimination sonochemistry 332 Cope reaction 1297 Hofmann 835 emission, and NMR 253 Cope reaction, and ammonium in the Stork enamine synthesis en-ynes, cyclization, metal salts 1383 587 catalyzed 985 elimination reactions, E1 versus initiation, and solvent effects enamides, torsional barrier 194 E2 1281 1278 enamine salts, and alkylation 587 elimination reactions, E1 versus IUPAC nomenclature 398–399 enamines, alkylation 587 E2 versus E1cB ketones, with organometallics and Michael reaction 587 1293–1294 1136 and microwaves 587 elimination reactions, E1 1280 leaving groups 1294 and N-alkylation 587 and carbocations 1280 and ionization 1294 and the Stork enamine reaction and ion pair mechanism 1281 and substitution 1294 587 and ion pairs 1281 mechanisms 1295 and tautomerism 102 and substitution 1280 metal induced, of dihalides to enamines, aromatization 1445 and Zaitsev’s rule 1281 alkenes 1318 chiral 705 mechanism, rate determining type II cleavage 1273 [2+2]-cycloaddition 1058 step 1280 1,4-, of allylic sulfoxides 1311 from aldehydes or ketones elimination reactions, E1cB, and of dihalides to alkenes, reagents 1199 carbanion mechanism for 1319 from amines 523, 1445–1446 1281 Peterson alkenylation 1191 and alkynes 927 mechanism 1281 photochemical 1273 by dehydrogenation 1445 elimination reactions, E2, and pyrolytic 1273, 1295 metal catalysts 1446 antiperiplanar and Bredt’s rule 1298 with ketones 1111 conformations 1276 and Hofmann’s rule 1298 enamines, from pyrroles 741–742 and conformations 1276 elimination reactions, radicals hydrolysis, mechanism 1098 and diastereomers 1274 1297 reaction conditions for and enantiopure alkyl halides rate of reaction 1297 formation 1113 1275 regiochemistry 1288 reduction with alane 1585 and Hofmann elimination 1306 reverse Cope 1308 Stork enamine reaction 586, and meso alkyl halides 1275 silyl-Wittig reaction 1191 1113 and strain 379 solvent effects 1286, 1294 enantioselective 587 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1990 SUBJECT INDEX

enamines, with acyl halides and temperatures 136 aziridine formation 1024 587 and tervalent stereogenic atoms Baeyer-Villiger reaction 1379 with alkyl halides 587 138 Baker’s yeast reduction of with isocyanates 1263 enantiomers, atropisomers 142 alkenes 1521 enamino esters 598 butan-2-ol 134 reduction of alkynes 1521 enamino ketones 1113 called enantiomorphs 134 Baylis-Hillman reaction 1151 coupling 805 definition of 134 benzoin condensation 1216 enaminyl radicals 1125 glyceraldehyde 148 boranes with aldehydes 1146 enantioenriched thioethers 508 IUPAC names 159 conjugate addition 967 enantioenrichment 172 levo and dextro 134 Cannizzaro reaction 1601 enantiomer formation, and the reaction rates 135 carbamates with aldehydes or Grignard reaction 1131 spiranes 144 ketones 1189 enantiomeric excess, and amides steering wheel model 151–152 carbene insertion 726 174 tartaric acid 135 carbenoids, and and NMR 173 enantiomorphs see enantiomers cyclopropanation 1075 definition, %ee 173 enantiomorphs 134 catalytic hydrogenation 1515 enantiomeric purity, and circular enantioselectivity, alcohols from chiral boranes 935 polarization of amines 505 chloroimine, with ketenes 1262 luminescence 175 alcoholysis of anhydrides 1228 Claisen rearrangement 1416 and GC 174 aldehydes, with enantioselectivity, conjugate and HPLC 175 organometallics 1137 addition 960 and isotopic dilution 175 with organozinc compounds of amines 979 and kinetic resolution 175 1140 cyclization, of alkene–acids and NMR 175 aldol condensation 1176–1178 1027 enantiomers see chiral alkenes from epoxides 1303 [3+2]-cycloaddition 1032 compounds, chirality metathesis 1428 cyclopropanation, alkenes 1072 enantiomers, adamantanes 140 with alcohols 917 Darzens condensation 1191 enantiomers, and 2n rule 159 alkynes anions with aldehydes Diels-Alder reaction 1040 and absolute configuration or ketones 1144 dihydroxylation 1008–1009 148 by hydroboration 1388 of alkenes 1007–1008 and allenes 144 allyltin compounds 1139–1142 ene reaction, carbonyl- 954 and biphenyls 141 amidation of alkenes 930 enolate alkylation 581 and bosons 135 amines to amine oxides, epoxidation 493, 1013, 1016 and catalysts 135 oxidation 1504 of alkenes 1016 and catenanes 130 with epoxides 522 epoxide hydrolysis 489 and circularly polarized light from imines 1555 epoxides with organometallics 135 aminohydroxylation 1020 572 and electrons 135 enantioselectivity, and catalytic formation of cyanoamines 1212 and enantiotopic atoms/groups hydrogenation 1514 enantioselectivity, Friedel-Crafts 183 and hydrosilation of conjugated alkylation 652 and Fischer projections 148 alkenes 1528 Grignard reactions 1131 and helical molecules 144 and nitrene formation 1022 Grignard reagents, Michael and isomers 134 and oxidative cleavage of diols addition with nitroalkenes and kinetic resolution 169 1463–1464 963 and plane of symmetry 136 and pinacol coupling 1595 halogenation of ketones 705 and mirror plane 136 and radicals 845 halogens, of aldehydes 704 and Mo2(OAc)4 155 and the Claisen condensation halolactonization 999 and molecular knots 130 1184 Heck reactions 812 and monocyclic compounds and the Michael reaction 955 Henry reaction 1186 179 and Ullmann reaction 798 hetero-Diels-Alder 1053 and nucleons 135 enantioselectivity, Arndt-Eistert Hiyama coupling 546 and plane polarized light 149 synthesis 1364 hydroamination of alkenes and polarizability 138 aromatic compounds, catalytic 1020 and prochiral 184 hydrogenation 1524 hydroboration 934–935 and pyramidal inversion arylation, active methylene of alkenes 935 138–139 compounds 820 hydrocyanation 1210–1211 and quadrivalent stereogenic aza-Claisen rearrangement hydroformylation 990 atoms 138 1418 hydrogenation of heterocycles and racemates 135 aza-Cope rearrangement 1410 1524 and rate of reaction 158 aza-ene reaction 953 hydrolysis of epoxides 489 and specific rotation 136 aza-Michael reaction 976 hydrosilation, of alkenes 941 and superimposability 138, 148 azidination 713 hydroxylation of hydrocarbons and symmetry 134 aziridination of alkenes 1024 1476 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1991

α-hydroxylation of ketones reactions 165 ENDOR, and radicals 252 1484 and N-heterocyclic carbenes ene reactions 869, 952 imines, with boronates 1165 275 ene reactions, and microwave with organolithium reagents [2,3]-rearrangement 1422 chemistry 334 1162 enantioselectivity, reduction of and oxygen 869 with silanes 1166 azirines 1024 and SeO2 oxidation 1482 in the Stevens rearrangement of chiral phosphine oxides and [1,5]-sigmatropic 1382 1586 rearrangement of insertion reactions 495 of ketones 1542 hydrogen 1401 enantioselectivity, of nitro compounds 1559 and steric acceleration 952 Jacobsen-Katsuki of oximes 1562 and the Prins reaction 1215 epoxidation 1017 of phosphine oxides 1587 aza-, enantioselective 953 Julia-Colonna epoxidation with boranes 1540 carbonyl-, enantioselective 1016 reagents 1545 954 ketenes, with imines 1262 enantioselectivity, reductive metal catalyzed 954 ketones, halogenation 707 amination 1121 Conia 954 with organometallics 1137 ring opening, aziridines 498 dienophiles 952 with organozinc compounds Robinson annulation reaction imino 953 1140 1179 intramolecular 953 Knoevenagel reaction 1188 Sharpless aminohydroxylation ionic liquids 952 β-lactones, from ketenes with 1019–1020 ketones, transannular 954 aldehydes or ketones 1261 Sharpless asymmetric mechanism 952 lactones, from diols 1494 epoxidation 1016 metal catalyst 952 Lewis acids, allylsilanes with [2,3]-sigmatropic temperature requirements 952 aldehydes 1209 rearrangements 1421 thiol, photoredox 953 Lossen rearrangement 1372 [3,3] sigmatropic typical functional groups 952 Mannich reaction 1124 rearrangements 1418 with imines 953 Meerwein-Ponndorf-Verley Staudinger reaction 1059 with nitrile oxides 953 reduction 1539 Stetter reaction 981 ene synthesis see ene reaction Michael addition 960 Stork enamine synthesis 587 ene-diynes, and Bergman of organometallic Strecker synthesis 1211 cyclization 1395 compounds 964–965 sulfinic ester preparation 504 electrocyclic rearrangement Mukaiyama aldol reaction 1182 sulfones and palladium 1395 nitrenes, insertion 715 catalysts 511 energy, activation see activation nitro aldol reaction 1186 sulfur ylids, and energy enantioselectivity, organoboranes, cyclopropanation 1207 chair-to-chair interconversion allylic addition to thia-Michael addition 978 195 aldehydes or ketones 1145 transamination 521 rotational barrier 141 organochromium compounds, transfer hydrogenation, and hyperconjugation 92–93 with aldehydes or ketones reduction of imines 1554 axial and equatorial substituents 1141 Wagner-Meerwein 197 organolithium reagents, rearrangements 1353 barrier, cause of 190 reactions 1135 Williams ether synthesis 492 measurement of 190 with alkenes 948 [2,3]-Wittig rearrangement pyramidal inversion 138 organometallics with CO2 1161 1422 energy, barrier, rotation in ethane deprotonation 733 enantiospheric 186 190 oxidation of thioethers to enantiotopic 184 and atropisomers 143 sulfoxides 1508 enantiotopic atoms 183 biphenyls 190 oxy-Michael reaction 978 isotopic labeling 184 diadamantyl compounds 190 oxyamination 1020 enantiotopic faces 185 rotation, MO calculations 190 Pauson-Khand reaction 986 enantiotopic, and to planarity, cyclopentane 203 Petasis reaction 1203 Cahn-Ingold-Prelog energy, bond 17 See also bond phospha-Michael addition 977 system 186 energy Pictet-Spengler reaction 655 definition 183 energy, bond dissociation, and pinacol coupling 1595 encapsulated osmium tetroxide, hyperconjugation 94 reagents 1595 and dihydroxylation of and small rings 208 pinacol rearrangement 1354 alkenes 1006 energy, bond resonance 64 protonation of enolate anions encounter complex 613 and hybridization 30 704 Encyclopedia of Reagents for energy, cascade, and photolytic Pummerer rearrangement 1603 Organic Synthesis 1626 cleavage 320 radical addition 1217 endocyclic alkenes 698 curve, diatomic molecules radical coupling of conjugated endohedral metals, and fullerenes 315–316 amides 874 92 substituted ethanes 190 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1992 SUBJECT INDEX

energy, cascade, and photolytic of carbonyl compounds, table and Weinreb amide 1174 cleavage (Continued) 98 and X-ray 248 cyclohexane conformations solvent effects 100 enolate anions, arylation 820 195 enol esters see esters, enol as bases 369 substituents 196 enol esters, with carboxylic acids as nucleophiles 479 energy, diagram, conformational, 1236 bases required for formation of ethane 189 enol ethers see ethers, enol 579 ethane 190 enol ethers, and transetherification canonical forms 100 torsion angle 191 496 Claisen condensation 248 energy, dissociation 29 See also conversion to amines 1124 conjugate addition 1179 dissociation (E)and(Z)isomers 721 coupling, palladium catalyzed carbocations, table 232 from alcohols 496 565 of radicals 258 from aldehydes or ketones dianions 479 energy, free see free energy 1189 E/Z selectivity 1174 energy, hydride shifts and oxidation to carboxylic acids enantioselective protonation carbocations 1351 1500 704 energy, levels, alternant oxidative cleavage 1472 enolate anions, ester 1253, 1417 hydrocarbons 69 enol ethers, silyl 579–580, 1181 See also Claisen benzyl cation/radical/carbanion from aldehydes 721 condensation, Dieckmann 70 from enolate anions 721 condensation odd and even alternant from ketones 720 and alkoxide bases 1255 hydrocarbons 69 metal catalyzed formation 721 enolate anions, formation of silyl radical anions 775 Mukaiyama aldol reaction enol ethers 721 energy, of butadiene 40 1181 from aldehydes or ketones of chair conformation 195 oxidative coupling to diketones 1172 of conjugation 42 1509 from carboxylic acid of light, and photochemistry with alkynes 944 derivatives 1183 314 with organolithium reagents from conjugate addition of potential see potential energy 722 organocuprates 961 rearrangements 1350 enol ethers, with from dialkylamides 721 π-energy 43 hexamethyldisilazane 721 from esters 1183 energy, resonance see resonance enol thioethers, from aldehydes or from Michael addition 895 energy ketones 1109 from silyl enol ethers 722 resonance 34, 207 enol–enol, stability 701 from the Michael reaction 955 energy, singlet carbenes 267 enolate anions 166, 703 halogenation 740 energy, strain 207 aggregation state 248 isomerization 1174 and molecular mechanics 205 aggregation, ab initio 248 ketones 1253 and trans cyclooctene 218 aldehyde 584 kinetic 721 calculations 207 aldol condensation 248, 580 magnesium 1174, 1178 energy, transition energies 474 alkylation 479, 576, 579 metal catalysts 583, 1175 triplet carbenes 267 and phase transfer 576, 582 Michael anions 1179 enol acetates 581, 722 chiral 579 monomeric 248 allylic, and Pd catalyzed enantioselective 581 nitro 1285 coupling 566 solvent effects 576 enolate anions, of carboxylic acid metal, and acyloxylation 871 allylation, SET 578 derivatives 1183 reaction with HCl 340 SN2 reactions 578 organocatalysts 584 with organocuprates 563 enolate anions, amide 194 organocatalysts 584 enol boranes 164 enolate anions, and aggregates oxidative coupling to diketones and synthesis 163 370 1509 enol borates 1176 and alkylation 248 preformed 956 enol borinates 1174 and Baldwin’s rules 289 resonance stabilized 579, 895 enol borinates see borinates and Claisen condensation 580, stability in solution 240 enol carbamates 921 1253 stereoselective 584 enol content, acetoacetamide 98 and enols 100 thermodynamic 721 acetoacetic ester 98 and Evans auxiliaries 1184 torsional barrier 194 amides 99 and HSAB 361 enolate anions, with acyl and carboxylic acids 98 and O-acylation 1252 hypofluorites 706 and conjugation 98 and O-alkylation 576 with aldehydes 248 and steric hindrance 98 and phase transfer 580 with alkyl halides 370, 479 and steric hindrance 98–99 and pKa 575 with chlorotrimethylsilane 721 esters 98 and α-protons 575 with disulfides 716 Fuson-type enols 99 and resonance 240, 1172 with halosilanes 721 Knoevenagel reaction 1187 and the Perkin reaction 1190 with ketones 248 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1993

with LiBr 248 enones, from allylic alcohols and dihydroxylation of aromatic with tosylcyanide 723 1482 compounds 1010 enolate condensation, and amide entgegen, and alkene and lactamization 1243 bases 579–580 nomenclature 176 and Michael addition 960 kinetic conditions 582 enthalpy 304 and molecular recognition 122 solvent effects 582 and free energy 283 and TEMPO oxidation of solvents 580 and kinetics 284 alcohols 1452 thermodynamic conditions and nitrenes 276 aromatic substitution 620 582 and reactions 283 carboxylic acids, reduction enolate formation, kinetic control and temperature 284 1547 721 cyclobutadiene 73 catalysts, cyanohydrins 1211 thermodynamic control 721 formal steric 220 esters, hydrolysis 1219 enolate reactions equilibrium of activation 285 Diels-Alderase 1037 conditions 582 reaction 1523 epoxide hydrolase 489 kinetic conditions 582 entropy, acyclic and cyclic ester hydrolysis 1220 thermodynamic conditions 582 molecules 284 for transesterification 1233 enolene rearrangement 1419 and acidity 368, 372 α-hydroxylation of ketones enolizable protons 703 and free energy 283 1483, 1486 enolization, and Grignard and kinetics 304 mediated aldol condensation reactions 1132 and pK 368 1172 enols, acyloxylation 871 and reactions 283 oximes, reduction to imines, acetoacetic ester 99 and ring size 286 enzymes 1564 aldehydes 98 and temperature 284 reduction of aldehydes or amphiprotic properties 701 and the intramolecular aldol ketones 1541 and aldol condensation 1178 condensation 1178 of aldehydes or ketones enols, and Bredt’s rule 752 cyclopropane to propane 286 1543 carbonyl halogenation 706 of activation 333 of imines 1553, 1555 enolate anions 100 and ring-closing reactions in supercritical carbon formation of furans from 286 dioxide 1542 diketones 1103 and Smiles rearrangement enzymes, resolution 169 hydrogen bonding 98, 108 837 YNAR-I and NADP-H 1530 and mechanisms 305 and substitution reactions catalyst 512 and nitrosation 711 422 catalyst, thioether formation and Stille coupling 718 elimination 1296 783 and tautomerism 97 entropy, [2+2]-cycloaddition eosin, and photochemistry of enols, by hydration of alkynes 915 reactions 1064 Aryldiazonium salts 832 electron delocalization 701 envelope conformation, and as photosensitizer 1056 fluorinated compounds 99 cyclopentane 202 eosin Y, aldehydes, conversion to from conjugated ketones 895 Envirocat-EPIC, Friedel-Crafts acetals 1102 from hydration of alkynes 914 acylation 659 ephedrine, and resolution 167 from ketones 1174 environmentally friendly, epimers, definition 159 Fuson-type 99 chemistry 390 episulfides see thiiranes hydrogen bonding 701 Mukaiyama aldol reaction 1181 episulfides, conversion to in the solid state 99 enynes, conversion to spirocyclic 2-chlorothio-esters 542 enols, intramolecular stabilization compounds 943 conversion to alkenes 1303 701 cyclization, metal catalyzed from diazonium salts 1208 isolation of 99 945 episulfones, and the lactone 100 cycloisomerization 1403 Ramberg-Backlund¨ malonaldehyde, hydrogen bond hydroboration 737 reaction 1317 108 via Stille coupling 719 from diazo compounds 1208 pentan-2,4-dione 100 with boronic acids 943 synthesis of 1317 preformed 1175 enzymatic, epoxidation 1013 episulfoxides, conversion to and aldol condensation 1178 hydrosols, nitriles 1100 alkenes 1303 and metal catalysts 1176 hydroxylation, of hydrocarbons epoxidation, and chiral dioxiranes solid state 99 1476 1014 stability 701 oxidations 1455 and chiral iminium salts 1015 stabilization 701 reduction, conjugated alkenes and conformation 1011 stable 98–99, 219 1530 and diethyl tartrate 1017 tautomerism 752 enzymes 122, 153, 184 and flow reactions 1011 tautomerization 327, 753 amides, from esters 1246 and hydroperoxides 1017 unstable 98 amines, oxidation to and hypochlorites 1017 with diazoalkanes 494 hydroxylamines, enzymes and ionic liquids 1011 with metal acetates 871 1503 and microwaves 1011 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1994 SUBJECT INDEX

epoxidation, and chiral dioxiranes Waits-Scheffer 1015 photochemical cleavage 262 (Continued) with peroxyimidic acid 1014 pinacol rearrangement 1356 and pinacol rearrangement epoxide hydrolase, enzyme 489 epoxides, reaction with alcohols 1500 epoxides, allylic, from allylic 496 and polyleucine 1016, 1206 alcohols 1367 with cyanide 601 and Prilezhaev reaction 1010 ambident substrates 482 with nucleophiles 497 and strained azetidinium ylid and Brook rearrangement 1110 with sulfur ylids 1205 1206 and leaving groups 465 with thiols 496 and supercritical carbon dioxide and formation of isonitriles 527 epoxides, reduction to alcohols, 1011 and Friedel-Crafts alkylation reagents 1531 and the Baeyer-Villiger reaction 573 to alkanes 1531 1016 and neighboring group with hydrides 1531 and titanium catalyst 1017 mechanisms 424 epoxides, silyl 547 epoxidation, asymmetric 1015 and sodium nitrate 523 via sulfur ylids 1205 and alkene structure 1017 and sparteine 1303 vinyl, rearrangement 1355 and allylic alcohols 1017 and Stork enamine reaction 587 metal catalysts 1356 and manganese salen and strain 208 vinylic 573 complexes 1017 and the Wittig reaction 524 SN2′ reactions 574 Sharpless 1016 and Williamson reaction 493 epoxides, with alkoxides 497 epoxidation, biomimetic 1013 epoxides, bicyclic 541 with alkyne anions 573 Cinchona-derived by modified Peterson with allylboranes 573 phase-transfer catalyst alkenylation 1192 with amide bases 523 1013 chiral 523 with amines, microwaves conjugated carbonyls 1015 epoxides, conversion to alkenes, 522 conjugated carbonyls, hydrogen electrolysis 1302 with ammonia 522 epoxide and base 1015 to alkenes, enantioselectivity with aromatic amines 522 conjugated carbonyls, 1303 with azide ion 523 mechanism 1015 to allylic epoxides 1302 with azide, Mitsunobu reaction dienes 1015 to chlorohydrins 541 523 dioxiranes, substituent effects to ketones, metal catalysts 1355 with boronates 594 1014 to lactones, metal catalyzed with boronic acids 595 dipeptide catalysts 1013 1359 with carbon dioxide 1106 enantioselective 493, 1013, to thiiranes 509 with carbon dioxide, flow 1016 epoxides, coupling with allyl reactions 1107 enzymatic 1013 silanes 547 with carbon monoxide 502 flow reactions 1016 deoxygenation 1531 with cyanides, metal catalyzed flow system 493 diastereoselectivity, from sulfur 601 Jacobsen-Katsuki 1017 ylids 1205 with dithianes 1438 epoxidation, Julia-Colonna´ 1016, enantioselective hydrolysis 489 with HF 540 1206 enantioselectivity, with sulfur with LiAlH4 1441 enantioselectivity 1016 ylids 1205 with LTMP 523 epoxidation, mechanism 1011 formation of aziridines 524 with organocuprates 572 metal catalyzed 1011–1012 from 1,2-diols 493 with organocuprates and Lewis molecular sieves 1017 from alkenes 1006 acids 572 epoxidation, of alkenes 493, from diols 493, 500 with organolithium reagents and 904–906, 1010 from halohydrins 424, 493 sparteine 1135 with oxaziridinium salts 1014 from halosulfones 1206 with organometallics 571–572 and kinetic resolution 171 from ketones or aldehydes with oxazine carbanions 591 anti-addition 905 1205 with peroxyacids 1434 reagents 1011 from selenium ylids 1205 with selenosilanes 497 steric hindrance 905 halogenation and with tosylamines 524 sterochemistry 905 organocatalysts 541 epoxy acids 1190 with sodium hypochlorite 1017 hydrolysis 489, 1006 epoxy alcohols 1135 epoxidation, organocatalysts enantioselective 489 epoxy esters, from halo esters, and 1013 in ionic liquids 541 aldehydes or ketones Payne 1380 intramolecular alcoholysis 497 1190 Sharpless, mechanism 1017 leaving group 567 epoxy hydrazones, base induced Shi- 1014 lithio, rearrangement 523 fragmentation 1323 stereochemistry 1206 meso 523, 1359 via Eschenmoser-Tanabe ring sulfur ylids, mechanism 1205 metal catalyzed azide ring cleavage 1323 tartrate 1017 opening 523 epoxy–alcohols, and Payne transition state 1011 metal catalyzed ring opening rearrangement 497 via sulfur ylids 1205 523 rearrangement 497 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1995

epoxy–ketones 1017 Erganzungswerks,¨ and Beilstein esterification, Mitsunobu reaction by Julia-Colonna epoxidation 1618 500 1016 ergost-7-en-3-one 380 of aldehydes with alcohols, rearrangement to diketones EROS 1626 metal catalyst 1497 1356 erythro nomenclature 160 reagents 1497 reduction to hydroxy ketones erythro/threo, and electrophilic of carboxylic acids 1229 1532 addition 893 esters see carboxylic acid esters with silanes 1541 ESCA, and carbocations 439 esters, acetoacetic, and alkylation EPR, and carbenes 268 Eschenmoser sulfide containing 577 and radicals 251–252 method 1324 acidity 364 equation, Brønsted catalysis 355 Eschenmoser variant, Claisen allene 921 duel substituent parameter 386 rearrangement 1417 allylic, isomerization 1367 Grunwald-Winstein, and solvent Eschenmoser-Claisen with aryl halides 564 effects 471–472 rearrangement, Claisen and base and metal catalysts and solvolysis 452 rearrangement 1417 1254 Schrodinger¨ 3 Eschenmoser-Tanabe ring and the Mitsunobu reaction Swain-Lupton 388 cleavage 1323 499 Swain-Scott 461 Eschenmoser’s salt, and Mannich aryl, conversion to nitriles 673 Taft 388 reaction 1124 boronate, from alkenes 937 wave 6 Escherichia coli JM109 oxidation 1387 equation, Hammett see Hammett (pDTG601), stability 737 equatorial, in chair conformations dihydroxylation of boronic, alkenyl 737 195 aromatic compounds 1010 by acyloxymercuration– equilibrium, acid–base 339 Escherichia Coli 1555 demercuration of alkenes aldol condensation 1179 Eschweiler-Clarke procedure 920 alkene metathesis 1425 1121 by cleavage of keto esters 757 and carbocations 439 ESR, alkyl halides and Grignard by oxidation of aldehydes 1496 and Cope rearrangement 1409 reagents 554 by oxidation of ethers 1488 and cyclohexane 195 and azoxy compounds 763 carbonate 1107 and HSAB 361 and Birch reduction 1525 carbonylation of alcohols and and pseudorotation 195 and captodative effect 256 alkyl halides 604 and rate-determining step 299 and carbenes 268 esters, carboxylic see carboxylic and SN1 reactions 414 and kinetics 301 esters and solvent acidity 353 and magnetic anisotropy 252 esters, carboxylic, alkylation 579 and tautomerism 97 and magnetic fields 252 and LDA 1183 and the Claisen condensation and methyl radical 259 and the Hunsdiecker reaction 1255 and radical 1348 886 and the Sommelet-Hauser and radical anions 763 by carbonylation of aryl halides rearrangement 835 and radical rearrangements 821 borane isomerization 1368 1348 carbonylation of alkyl halides carboxylic acids and alcohols and radicals 251–252, 256, and alcohols 604 1228 421, 847 cleavage with LiI 542 carboxylic acids, water, and and splitting 252 conjugated, from boronic esters alcohols 1219 and unpaired electrons 253 743 constant 143, 285 ESR, bromonium ions 898 coupling with organometallic and atropisomers 143 Grignard reaction 1134 reagents 563 and Brønsted equation 356 methyl radical 259 from alkyl halides 604 and free energy 383 ester enolates, alkylation 584 steric hindrance to formation of and solvent acidity 354 ester hydrolysis, enzymatic 1220 378 and the Hammett equation gas phase 1220 types of bases 1183 381 lipase 1220 with Grignard reagents 1157 cyclopropylcarbinyl versus mechanism 1220 with Metal carbene complexes cyclobutyl cations 1356 microwaves 1220 1203 enolate reactions 582 phase transfer 1220 with organolithium reagents ester hydrolysis 1219 structural variations 1220 1157 formation of hydrates 1095 ultrasound 1220 with organometallics 1158 isomerization of alkenes 1314 ester, enolate anion 1417 esters, conjugated, and keto-enol 701 ester intermediates, and phosphonate ester ylids keto-enol/enolate anion 703 oxidation–reduction 1441 1201 organolithium-alkyl halides ester oximes, with acids 1377 conjugate addition of lactams 238 ester, manganate 1006 977 pyrolysis of alkyl boranes 1314 ester, vinyl 920 organometallics 1143 Schlenk 245 esterases, and resolution 169 with Petasis reagent 1202 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1996 SUBJECT INDEX

esters, conversion to amides 1245 esters, imino see imino esters reagents for preparation 504 biocatalysts 1246 esters, imino, and the Chapman with halide ions 535 enzymes 1246 rearrangement 1435 with organocuprates 556 flow reactions 1246 inorganic, decomposition to esters, thiono see thionoesters ionic liquids 1246 alkenes 1305 vinyl, and transesterification mechanism 1247 from alcohols 504 1233 metal catalyzed 1246 keto, decarboxylation 753 vinyl with aldehydes 1366 microwaves 1246 ketones 1183 with aldehydes 1183 esters, conversion to hydrazides malonic, alkylation 576 with base 1417 1247 metal, and dihydroxylation of with boranes 1158 to hydroxamic acids 1247 alkenes 1009 with ketones 1255 to nitriles 601 methyl, from oxazolidinone with Mo peroxide, esters, coordination with SnCl4 amide 1234 α-hydroxylation of enolate 368 from trimethyloxonium anions 1483 esters, decarboxylation 753 tetrafluoroborate 1234 with MoOPH, α-hydroxylation to alkenes 1303 esters, mono, of sulfuric acid of enolate anions 1483 solvent free 1304 504 esters, xanthate see Chugaev esters, dicarboxylic acids, and nitrite, from alcohols 504 reaction Stobbe condensation 1183 esters, of inorganic acids, esters, xanthate see xanthate enamino 598 hydrolysis 485 esters enol, from alkynes 920 esters, ortho see ortho esters esters, xanthate, and the Chugaev enol, from alkynes, metal esters, osmate 1006 reaction 1304 catalyzed 920 esters, phenylseleno 716 Etard´ reaction 1478 enolate anions, and O-acylation phosphate 505 and chromyl chloride 1479 1252 phosphonate 505 and radicals 1481 esters, formate see formate esters and ylids 1198 mechanism 1479 esters, formation by SN2 reactions from alcohols 504 ethane, conformational energy 499 from alkenes 929 diagram 189 formation with microwave from alkynes 929 conformations 190 irradiation 499 polymer bound 1198 derivatives, conformation 191 esters, from alcohols 606 vinyl 931 energy barrier to rotation 190 from alcohols and ketenes 919 with Lawesson’s reagent energy diagram 190 from aldehydes 1197, 1496, 1305 heat of atomization 29 1602 esters, phosphonic, with Grignard substituted, conformational from alkenes 920 reagents 567 energy 190 with carboxylic acids 920 with thiols 1237 supercritical, hydrogenation, from alkyl halides 605 esters, proline and abrine, aromatic compounds metal catalyzed 605 catalysts 310 1523 from amides 1234, 1584 pyrolysis 1303 ethanedial, conformation 193 from borates 606 reagents for reduction 1548 ethanolysis see solvolysis from dithioesters 1233 rearrangement 675 ethanolysis, of alkyl tosylates, rate from hydrocarbons 1477 esters, reduction to aldehydes of reaction 452 from ketones 1103 1551 SN2 reaction, with alkyl halides from organometallics 738 to aldehydes, reagents 1551 377 esters, halo, with aldehydes or to alkanes 1574 ethene see ethylene ketones 1190 to ethers, reagents 1579 ethers, acidity 364 with alkoxide bases 1190 esters, seleno 1227 alkoxymercuration– with boranes 593 by carbonylation 821 demercuration 917 with hexamethyldisilazide esters, solvolysis of, and NMR alkynyl, hydration of 916 1190 412 ethers, allylic aryl, rearrangement esters, hydrogenolysis 1575 sulfamate 714 1415 and the Barton-McCombie sulfinate, from sulfinyl allylic vinylic, and reaction 1576 chlorides 511 [3.3]-sigmatropic reagents 1576 sulfinic, enantioselective rearrangement 1406 esters, hydrolysis 1219 preparation 504 allylic vinylic, and the Claisen mechanism 296 esters, sulfonate see sulfonate rearrangement 1415 catalysis, by cyclodextrins esters allylic, cleavage with Grignard 1219 esters, sulfonate, DMSO oxidation reagents 571 by metal ions 1219 1490 allylic, conversion to aldehydes catalysts 1219 from alcohols 504 1384 equilibrium 1219 from alkyl halides 505 allylic, pyrolysis 1329 rate constants 384 from sulfonyl halides 504 allylic, with organolithium rates 379 mechanism of formation 504 reagents 1384 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1997

ethers, and ionic liquids 491 lariat ethers 120 and the Boord reaction 1320 and microwaves 491 macrocyclic 119 metal catalyzed elimination to and the Mitsunobu reaction 495 NMR and guest–host alkenes 1320 and the Wittig rearrangement interactions 121 ethers, halomethyl, with boranes 1384 podands 120 1386 aryl allyl, Claisen starands 120 hydrogenolysis 1573 rearrangement of 2-allyl ethers, cyclic 492 hydrolysis of 494 phenols 1415 cleavage 540 hydroxy 497 and microwave irradiation from alcohols 866 lactim see lactim ethers 781 with lead tetraacetate, lariat 120 and phase transfer 781 mechanism 866 MEM 492 from alkoxides 781 from epoxides 497 MOM 492 photochemical preparation large rings 493 nitrate, from alcohols 504 from aryl nitriles 794 oxidation to lactones, reagents oxidation to carboxylic esters azacrown 118 1488 1488 base-induced elimination 1301 reagents from oxidation of oxime see oxime ethers benzylic, and Williamson ether alcohols 866 photochemistry 317 synthesis 490 reduction of lactones 1580 ethers, propargylic, conversion to hydrogenation 540 transetherification 496 dienes 1301 by dehydration of alcohols 495 with organolithium reagents formation of allenes 1320 by insertion reactions of 1301 protection of alcohols 492 alcohols 729 ethers, diaryl 492, 782 reduction 1573 by reduction of thiono esters preparation 781 of esters, reagents 1579 1580 ethers, diphosphacrowns 118 reagents 1573 ethers, cleavage 502, 540 ethers, enol see enol ethers substrates 1573 and ionic liquids 540 ethers, enol, addition of hydrazoic ethers, reductive alkylation of phase transfer 636 acid 931 aldehydes 1104 structural parameters 1301 alkoxymercuration 918 ethers, silyl 492 with alkylsilanes 540 by rearrangements of trimesityl ethers, silyl enol 579–580, 1181 with HBr 486 compounds 328 See also enol silyl ethers with HCl 486 from acetals or ketals 1103 and Michael addition 956 with HI or HBr 540 from enols 494 conversion to nitriles 601 with lithium diphenylphosphide from esters 1202 hydrolysis 489 520 hydrolysis 486, 488 to α hydroxylate ketones 1484 with organometallics 570 metal catalyzed reactions 581 with acetals 570 with sulfuric acid 486 silyl, Mukaiyama aldol reaction with aldehydes and chiral with thiolate anions 509 1181 boranes 1182 ethers, crown 117–122 See also ethers, formation, and SN1 ethers, silyl, reaction with fluoride crown ethers reactions 491 ion 493 and ambident nucleophiles 481 and SON2 mechanism 783 solvents see solvents, ether and chirality 147 transition metal catalysts 491 solvents, and Grignard reagents and complex formation 117 ethers, from acetals 570 245 and fluorination of alcohols 539 from acetals or ketals 1574 tertiary alkyl, and Williamson and hydrogen bonding 119 from alcohols 494 ether synthesis 491 and hydrogen bonds 121 and trifluoroborates 494 tetrahydropyranyl, oxidation, and metal ions 117 from alkenes and alcohols and zeolites 1459 and molecular recognition 121 916 thiacrown 118 and phase transfer catalysis and phenols 916 transetherification 496 476 from alkoxides 494 trimethylsilyl, oxidation 1458 and spherands 119 from alkyl sulfates 494 with O2 1459 as cavitands 119 from diazo compounds 494 ethers, vinyl see ethers, enol; as hosts 119 from esters 1580 vinyl ethers bicyclic 119 from Grignard reagents 570 ethers, vinyl, and radical binding metals 119 and peroxides 734 cyclization 975 chiral 118 from inorganic esters 493 and Wittig rearrangement 1384 chiral, and resolution 168 from onium salts 498 cleavage by Grignard reagents cryptands 120 from oxonium salts 541 571 cryptaphanes 120 from phenols 494–495 hydrolysis 488 guest and host 117 from thionoesters 1580 with alcohols and halogens hemispherands 120 from trifluoroborates 783 997 in guest–host interactions 119 ethers, halo 1128 with thiols 922 ion binding 119 and elimination with Grignard ethers, Williamson ether synthesis ion–dipole interactions 121 reagents 1321 490 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

1998 SUBJECT INDEX

ethers, with alkyl halides 503 halogen-metal, and isotopic labeling 1362 with alkynes, microwave organocuprates 557 mechanism 1362 irradiation 939 hydrogen 629 trapping cyclopropenone 1363 with anhydrides 502 hydrogen-lithium 806 Favorskii, quasi-, rearrangement with Grignard reagents 571 R2Mg and R2Hg compounds 1363 with mineral acids 540 238 Fe/9-azabicyclo[3.3.1]nonan-N- with organolithium reagents exciplex formation 1063 oxyl, oxidation of alcohols 1301, 1384 in photochemistry 325 1452 Wittig rearrangement 1384 excitation, electronic 316 Felkin-Anh model 1088 with organosodium reagents excited molecules, physical and asymmetric synthesis 163 1301 processes 323 and diastereoselectivity 163 with oxonium salts 503 excited states, and photochemistry and radical addition to dienes with oxygen 867 318 899 with sulfuric acid 486 ethylene 319 Fenton’s reagent 865, 880 ethers, ynol 920 fluorescence 321 and coupling 874 ethylene oxide, strain 208 formaldehyde 319 ferricyanide, K, and ethylene, and electronic structure intersystem crossing 322 dihydroxylation 1009 16 Jablonski diagram 321 ferrocene 66, 115 and hybrid orbitals 9–10 photosensitization 323 ferrocene, bonding 66 and π orbitals 9–10 physical processes 320 ferrocene, structure 115 and π-bonds 43 pK of naphthol 319 ferrous sulfate, and peroxides canonical forms 47 promotion 321 865 complex with silver 115 properties 319 field effect constants 384 excited state 319 exhaustive alkylation, and field effects 20, 48 structure 16 quaternary salts 513 and acid strength 362 ethylenediaminetetraacetic acid, exocyclic alkenes 698 and aromatic compounds 22 and Udenfriend’s reagent extended anomeric effect 1088 and base strength 362 865 extinction coefficient 316 and benzyne reactions 778 ethyllithium, and iodoethane, and UV 315 and bond polarization 21 NMR 254 extra-cyclic resonance energy 62 and carbanions 241 ethylmagnesium bromide, and extraction system, and flow and carboxylic acids 21 X-ray 245 chemistry 336 and hybridization 22 ethylmercuric chloride 248 extrusion, of carbon dioxide and pKa 362 ethylpyridinium tetrafluoroborate, 1323, 1325, 1332 and reactivity 375 ionic liquids 394 from lactones 1331 and sterochemistry 905 ethyne, and orbitals 11 extrusion, of carbon monoxide and substituent effects 454 and triple bonds 11 1324, 1331 and the Hammett equation 381 σ electrons 11 and Diels-Alder reaction 1324 and ylids 241 ethynyl benziodoxolone 508 extrusion, of nitrogen 1032, 1330 and σ values 385–386 europium compounds, chiral shift and diradical 1330 and σ* values 385 reagents 174 mechanism 1330 benzoic acids 363 eutectic solvent, deep see deep of sulfur dioxide, from sulfones +I and –I 21, 375 eutectic solvent 1331 +M and –M, table 376 eutectic solvent, deep, aldol reactions, and elimination 1273 of groups 22 condensation 1177 and tetrahedranes 1331 Fieser’s Reagents for Organic deep, and Williamson ether definition 1329 Synthesis 1629 synthesis 490 Finkelstein reaction 534 deep, Paal-Knorr reactions F and R values, table 386 and phase transfer 535 1114 F strain, and acidity 366 metal catalyzed 534 thio-Michael addition 978 F values, and σ values 387 first order rate constant 302 Evans auxiliaries, with enolate face strain, and acidity 366 first order rate law 301 anions 1184 faces, diastereotopic 185 and neighboring groups 422 even alternant hydrocarbons see facial selectivity see selectivity first order reactions 297, 412 alternant hydrocarbons Far UV 318, 901 and racemization 414 exaltations, nucleus-independent and photochemistry 314 Fischer carbene complexes, and chemical shifts, arynes fatty acids, decarboxylation 754 Dotz¨ benzannulation 774 hydroxylase-BM3, oxidation of 1079 exchange reactions 505 hydrocarbons 1476 with alkynes 1079 amine salts with amides 1247 Favorskii reaction 1144 Fischer carbene compounds 1071 carboxylic acids, with amides Favorskii rearrangement 1361 Fischer indole synthesis 1419 1236 bond migration 1362 and [3,3]-rearrangement 1420 with esters 1236 cyclopropenone intermediate and benzyne 1420 and acyl halides 1251 1362 and isotope labeling 1420 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 1999

flash photolysis, of bromoform formation of aziridines 1024 and Tamao-Fleming oxidation 269 formation of diazoesters 713 499 of diazomethane 268 Grignard reagents, with nitriles metal, fluorinating agents 535 Flash vacuum pyrolysis see FVP 1168 reaction with silyl ethers 493 and vinylcyclopropane halogenation of ketones 707 fluorides, acyl 1251 rearrangement 1407 Henry reaction 1186 from acyl chlorides 647, 1251 of halocyclopropanes 1358 hydroformylation 989 from anhydrides 1251 of phosphorus ylids 1308 hydrogenation 1197 from KF and acyl halides flow reactions 336–338 hydrolysis of nitriles 1100 1251 alkyl halide coupling 559 hydrometallation 939 defluorination 1570 amide hydrolysis 1224 iodination 337 electrolysis 1570 from aldehydes 1498 flow reactions, library synthesis from aniline, and flow reactions from esters 1246 337 647 amination of aryl hydrazines metal alkyne with aryl halides aryl, with amines, and 637 816 ultrasound 786 amines with esters 1246 microwave-assisted 337 fluorinating agents 534 from nitro compounds 1560 nitriles from carboxylic acids gem, and DAST 1128 and [2+2]-cycloaddition 1060 601 propargylic 539 and [3+2]-cycloaddition 1031 O and S alkylation 508 fluorinated alkenes 1066 and boronic acids 736 Oppenauer oxidation 1450 fluorinated compounds, enol and carboxylation of oxidation, of alcohols, with content 99 organometallics 743 H2O2 1455 fluorinating agents 498, 534 and continuous liquid–liquid Paal-Knorr pyrrole synthesis fluorination 858 separation 337 1114 aromatic compounds 647 and diazo esters 1071 Pauson-Khand reaction 986 aromatic, and hypervalent and difluorocarbene 1069 phenols, from aryl halides 780 iodide 647 and hydroarylation of alkynes photochemical 337 aryl, Schiemann reaction 647 950 preparation of aziridines 526 decarboxylative 491 and hydroboration 933 preparation of diazomethane of aldehydes or ketones 705 and molecular cage macrocycle 1031 of alkanes 857 337 preparation of Grignard of alkenes 911 and N-heterocyclic carbenes reagents 548 of amides 764 275 preparation of organolithium of boranes 740 and organolithium formation reagents 548 radical 861 337 reduction of imines 1554 reagents 705 and organometallics 743 reductive amination 1120 SNAr 792 and oxy-Cope rearrangement SNAr, heterocycles 770 with polyhydrogen 1409 Suzuki-Miyaura coupling fluoride–pyridine 1251 and pinacol coupling 1594 800 fluorine, hydrogen bonding 111 and radical cyclization 975 thiols with aniline derivatives and halogenation of alkenes and the Bamford-Stevens 784 994 reaction 713 ultrasound, and Barton and keto-enol tautomerism 99 and the Heck reaction 811 decarboxylation 755 fluoro-2,4,6-trimethylpyridinium and the Petasis reaction 1202 Wolff rearrangement 1365 triflate 647 flow reactions, aniline to aryl flow reactors 336 fluoroborate, acyl and acetic fluorides 647 and biocatalytic resolution 337 anhydride 1025 arylation of alkenes 831 and moving-bed chromatograph fluorophenylcarbene 271 arylation of amines 786 337 fluorosulfonic acid-SbF5, aryldiazonium salts 647 and UV, formation of radicals superacid 347 azo compounds 638 338 fluorosulfuric acid, and cation boronates from organometallics preparation of ketenes 338 stability 225 792 preparation of phosgene 337 fluoroanthrene, from conversion of aldehydes to fluids, and flow chemistry 336 benzobiphenylene 1399 amides 1498 fluoranthene, and complex fluxional inversion 138 coupling, palladium catalyzed formation 121 fluxional isomerization 179 565 fluorene, apK 64 fluxional structures, and Cope cyclopropanation 1072 fluorescence, and promotion 323 rearrangement 1412 diazotization of amino acids and radiationless processes 322 FMO (frontier molecular orbital) 337 characteristics 322 1031 Diels-Alder reaction 1038 fluoride ion, acyl, from HF and and [3+2]-cycloaddition 1031 epoxidation 493, 1016 anhydrides or acyl halides and dipolar addition 1029 epoxides, with carbon dioxide 1251 forbidden and allowed reactions 1107 and silanes 966 1049 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2000 SUBJECT INDEX

forbidden reactions, aryl 663–666 intrinsic 292 [2+2]-cycloaddition 1063 Friedel-Crafts catalysts 665 kinetic versus thermodynamic, forbidden thermal cycloadditions Gatterman reaction 665 energy profile 290 1050 indoles 665 linear 383 forbidden transition, in N-, of lactams 1250 of activation 285 photochemistry 316, 320, of alkenes 720 profile 285 323 of amines 1247 profile, gas phaseN S 2 reactions formal charge, and bonding 17 of ketones 720 408 formal steric enthalpy 220 pyrroles 665 spontaneous reactions 283 formaldehyde, acid catalyzed Vilsmeier-Beckman reaction free radical addition 281, 896 addition to alkenes 1213 664 and atom transfer 896 and HCl 656 formylcarbene, lifetime 271 and chain termination 897 and the Eschweiler-Clarke formic acid catalyzed and polymerization 897 procedure 1121 hydroformylation, of mechanism 896–897 and the Mannich reaction 1123 alkenes 989 stereoselectivity 897 and the Prins reaction 1213 four center transition state, rearrangement 282 and Tollens’ reaction 1193 electrocyclic ring opening substitution see substitution and trioxane 1259 1391 free radicals see radicals excited state 319 four-center mechanisms, and free-energy profile, reaction with with glycoluril 132 hydroboration 933 intermediates 287–288 with phenols and amines 671 fractional crystallization, and reaction with no intermediates formamides, and phosphorus resolution 166–172 287–288 oxychloride 720 fractional distillation, and freezing point depression, and and the Leuckart reaction 1121 diastereomers 168 Grignard reagents 246 and the Wallach reaction 1121 and resolution 168 and organometallics 245 and Vilsmeier-Haack reaction fractional recrystallization, and Fremy’s salt, oxidation of 663 diastereomers 168 cathecols and carbonylation of amines 764 and resolution 196 hydroquinones 1459 conversion to isonitriles 527 fragmentation, and abnormal frequency factor, and rate law from isocyanides 1264 Beckmann rearrangement 303 from isocyanides, mechanism 1326 Friedel-Crafts, acylation 641, 1264 carbenes 274 658, 682 hydrolysis to amines 1258 definition 1321 acylium ions 659 with acetals 720 dialkylamino halides 1321 and activated rings 659 formamidines, bases 349 mechanism 1321 and acyl halides 661 formation of chiral amines 590 of epoxy hydrazones, base and deactivated aromatic rings formate esters, from cyanuric acid induced 1323 659 1234 Franck-Condon principle 320 and deactivated rings 659 formates, chloro see free energy see energy and IR 661 chloroformates free energy, acid–base reactions and Lewis acids 659, 661–662 formates, ammonium with amines 356 and microwaves 659, 662 764 amide hydrolysis 377 and protonic acids 659 reduction of aldehydes or and acidity 373 aza- 663 ketones 1541 and Brønsted equation 356 complex formation 661 formic acid, and the Koch-Haaf and carboxylic acids 372 Envirocat-EPIC 659 reaction 982 and catalysis 295 formation of aldehydes 663 and the Wallach reaction 1121 and enthalpy and entropy Fries rearrangement 659 conformation 193 283 Haworth reaction 660 formation of formates 1541 and equilibrium constant heterocycles 660 from chloroform 484 383 internal 660 with Grignard reagents 743 and Grunwald-Winstein magnetically separable 662 with hydroxylamine and relationship 383 Friedel-Crafts, acylation, aldehydes 1117 and intermediates 286 mechanism 660–661 with iodine and amines 1239 and kinetic control 290 of alkenes 719 with reductive alkylation 1119 and reaction intermediates phospha- 663 formic anhydride 663 287–288 regioselectivity 662 stability 1241 and SN2 reactions 409 reusable catalyst 662 formula periodic table 58 and solvent acidity 354 ring closure 660 for benzenoid polyaromatics 58 and solvent effects 471 solvent free 659 formyl chloride 663, 1251 and thermodynamic control thiophenes 659 formylation, and formamides 720 290 Vilsmeier-Haack reaction 663 aromatic compounds 663, 665 and transition states 291 with cyclic anhydrides 660 mechanism 664 equation 283 with formamides 663 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2001

Friedel-Crafts, alkylation 648, formation of aryl carboxylic fulminates, with aromatic 1336 acids 667 compounds 672 alkyl migration 680 formylation 665 fulminene 85 and activating groups 649 Friedel-Crafts, cation, formylation fulminic acid, [3+2]-cycloaddition and alkenes 651 663 1031 and carbocation rearrangement Friedel-Crafts, cyclization 654 fulvalenes 68 651 Bischler-Napieralski reaction and aromaticity indices 68 and carbocations 653 655 fumaric acid 178 and epoxides 573 Bradsher reaction 654 fuming sulfuric acid, with and heterocycles 649 Pechmann condensation 654 aromatic compounds 639 and Markovnikov’s rule 651 Friedel-Crafts, formylation 663 functional group compatibility, and metal catalyst 650 regioselectivity 664–665 and alkene metathesis and microwaves 650 and Fries rearrangement 675 1428 and primary halides 651 and nitrobenzene 648 Darzens condensation 1191 and reversal 682 Friedlander¨ quinoline synthesis functional groups, and active and tight ion pair 652 1113 methylene compounds and vinyl groups 651 and microwaves 1113 575 arylboronic acids 650 and pyrylium ions 1113 and catalytic hydrogenation calcium catalyst 649 Fries rearrangement 675 1514 carbocations 651 and crossover experiments 676 and CIP rules 149–152 carboxylic esters 650 and Friedel-Crafts reaction 675 and nucleophilic strength 464 catalyst 649 and ionic melts 676 compatible with organocuprates catalyst free 652 and LDA 677 962 contra 649 and Lewis acids 675 ease of reduction 1511 cyclodehydration 653 and microwave spectroscopy for the Knoevenagel reaction deactivating groups 648 676–677 1187 electrophile 651 and UV 676 oxidation state 1439 enantioselectivity 652 anionic 677 type, synthesis of 1641 graphene mediated 649 ate complex formation 676 functional groups, reactivity with heteroaromatic 648 crossover experiments 676 Dibal 1533 IR and NMR 651 Friedel-Crafts acylation 659 with Red-Al 1533 kinetics 652 intramolecular 676 with Selectrides 1535 Friedel-Crafts, alkylation, mechanism 676 with sodium borohydride 1533 polyalkylation 652 metal catalyzed 676 reduction 1512 polyphosphoric acid 654 para migration 676 furan, and aromaticity 62 pyrrole 652 regiochemistry 676 Diels-Alder reactions 1055 reagents 650 thia- 677 from diketones 1103 rearrangement 650 Fries, photo see photo-Fries halogenation 645 regioselectivity 650, 652 Fritsch–Buttenberg–Wiechell Paal-Knorr furan synthesis reversal 681 rearrangement 1313 1114 intramolecular 681 frontier electron density 891 resonance energy 63 mechanism 682 frontier molecular orbitals see SEAr reactions 623 temperature dependence FMO furanose compounds, and 681 frontier molecular orbital method tautomerism 103 reverse, and isotope labeling 1046, 1392 fused aromatic compounds, and 682 Diels-Alder reaction 1045 bond distance 60 SN2 mechanism 652 electrocyclic rearrangements and resonance energy 60 stereochemistry 652 1390 SEAr reactions 624 trifluoroborate salts 653 frustrated Lewis pairs 1537, 1554 fused ring aromatic compounds with alcohols 649 as catalysts 311 51 with alkyl halides 648 conjugated alkenes 1530 Fuson-type enols 99 with ketones 653 Fukui function 891 FVP (flash vacuum pyrolysis) with oxiranes 650 Fukuyama coupling 1158 1308, 1407 with sulfonate esters 650 fulgide, and helical chirality 145 polycyclic aromatics 1399 Friedel-Crafts, arylation 657 fullerenes 91 Scholl reaction 657 and aromaticity 91 Gabriel synthesis 529 Friedel-Crafts, catalysts, addition and MO calculations 91 Ing-Manske procedure 530 of alkyl halides to alkenes and rotaxanes 127, 131 galvinoxyl, radical inhibitor 969 1003 bowl-to-bowl inversion 92 gas chromatography see GC and halo 1005 hetero 91 gas electron diffraction 98 and halo ketones 1004 homofullerenes 92 gas phase acidity 371 and haloalkylation 656 molecular stoppers 131 of alcohols 372 dehalogenation 1569 synthesis 92 gas phase basicity 371 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2002 SUBJECT INDEX

gas phase, and ozonolysis 1470 Gif system 1477 green, aromatic nitration 631 ester hydrolysis 1220 Gilman reagents 555 See also aza-Michael reaction 976 SN2 406 organocuprates nucleophilic substitution 403 SN2, free energy profile 408 Gilman reagents 555 Grignard-Barbier reaction 1130 gas vacuoles, and sonochemistry Girard’s reagent P, and Grignard reagents 1129, 1153 331 hydrazones 1117 See also organomagnesium Gatterman amide synthesis 667 Girard’s reagent T, and and deep eutectic solvent 1130 Gatterman method 833 hydrazones 1117 and enolization 1132 mechanism 833 Glaser reaction 876 and ionic liquids 1129 and the Hoesch reaction 672 and the Hay reaction 876 and metal catalysts 1130–1131 formylation 665 in ionic liquids 876–877 and radicals 257 mechanism 666 in supercritical carbon dioxide and reduction 1132 Gatterman-Koch reaction 666 876–877 mechanism 1132 reverse 683 mechanism 877 and Reformatsky reaction 1153 Gattermann reaction 827 glucosides, and the anomeric and SRN1 mechanisms 1134 gauche conformations 190–191 effect 200 and the Barbier reaction 1130 See also conformations glyceraldehyde, and absolute and Wittig type reactions 1132 and elimination 1279 configuration 148 diastereoselectivity 1131 gauche effect 191 oxidation to glyceric acid, and ESR 1134 GC (gas chromatography) and chirality 148 formation of enantiomers 1131 determining absolute glyceric acid, and chirality 148 intramolecular 1131 configuration 153 chiral, from glyceraldehyde mechanism 1133 and diastereomers 168 148 N-heterocyclic carbene and enantiomeric purity 174 glycerol-3-photphate catalysts 1131 and resolution 168 dehydrogenase 1435 protonation 1569 geared molecules 219 glycidic acids, decarboxylation to retro 1130 gears, molecular, and chiral axis aldehydes 753 Schlenk equilibrium 1133 152 glycidic esters 1190 See also SET mechanism 1133 gegenion, of carbocations 225 epoxy esters solid phase 1129 gel-entrapped base, Henry glycolaldehyde, conformation 1,2- versus 1,4-addition reaction 1185–1186 193 1129–1130 gelators 128 glycols see diols with ammonium chloride 1129 gem-dihalides see dihalides glycoluril, with formaldehyde with organotitanium reagents gem-dihalides, from amines 1492 132 746 gem-dimethyl effect, glyoxals, and the benzoin Grignard reagent–amine complex halolactonization 999 condensation 1216 747 gem-dimethyls, by hydrogenation benzoin condensation 1216 Grignard reagents 548 of cyclopropanes 1531 gold catalyst, cyclization of alkyne addition to alkenes 938 from cyclopropanes 1531 acids 1027 amination 741 geminal bond participation 1403 gold, vinylidene 728 Grignard reagents, and alkyl general acid catalysis 355, 487 Goldberg reaction 789, 831 halides, SN2 mechanism generalized population analysis intramolecular 831 554 112 Gomberg-Bachmann pinacol and arylboronic acids 735 genomic salmon testes DNA, and synthesis 1593 See also and boiling point elevation 246 the Michael reaction pinacol coupling and CoCl2, and radical 955 Gomberg-Bachmann reaction, cyclization 974 geometric structure, carbocations, mechanism 833 and conformational stability and migratory aptitudes Gomberg-Bachmann-Hey 247 1342 reaction, copper catalyzed and dialkylmagnesium 1132 geometry, alkenes, and 832 and elimination of halo ethers photochemistry 328 Google searching 1607, 1614 1321 and molecular conformation Gossypium hirsutum, oxidation of and ether solvents 245 205 hydrocarbons 1476 and flow reactions 548 hydrogen bonds 108 graduate, textbooks of organic and freezing point depression of carbenes 269 chemistry 1627 246 of electrophilic allylic graphene mediated Friedel-Crafts and HMPA 247 rearrangement 694 alkylation 649 and ketyl dimerization 1134 of hydrogen bonds 108 graphite 91 and microwaves 1129 of propellanes 212 graphite ribbons see phenacenes and NMR 246–247 of radicals 259 green catalysts, amines, oxidation and oxygen 734 gerade orbital 6 to nitriles 1460 and peroxides 735 Gibbs energy, and microwave green chemistry 338, 390 and radicals 1134 chemistry 335 green solvents 393 and reagents 562 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2003

and Schlenk equilibrium preparation and solvents 748 with tellurium 738 245–246 reaction with carbon monoxide with vinyl halides 553 and solvents 246 551 with ytterbium compounds 571 and the Boord reaction 1321 SET mechanism 748 Wurtz-type coupling 1132 and the Bruylants reaction 568 SN2′ reactions 551 X-ray diffraction 245 and the Wurtz reaction 880 solution structure 246 grinding, and reactions 338 and THF 247 solvation 245 Grob fragmentation 1322 and Wurtz coupling 747 solvents 747 and Cinchona alkaloids 1322 Grignard reagents, aryl 246 structure 245 mechanism 1322 hydrolysis 686 and concentration 246 ground state, and excited state as a base 350, 730, 747 sulfonyl sulfur, nucleophilic 314 bonding 245 substitution 1266 and photochemistry 314 cleavage of allylic ethers 571 Weinreb amides 1159 groups in substitution reactions, cleavage of vinyl ethers 571 Grignard reagents, with acetals table 457 complex formation 245 570 Grovenstein-Zimmerman conjugate addition 1129 with acid derivatives 1154 rearrangement 1353 conversion to amides 743 with active hydrogen Grubbs’ catalyst, and alcohol coordination with magnesium compounds 747 oxidation 1458 1132 with aldehydes 1129 I and II, for alkene metathesis coupling 551 with alkyl halides, mechanism 1427 of alkyl halides 550 553 Grunwald-Winstein equation, and with alcohols 568 radicals 554 solvent effects 471–472 with aryl halides 796 SET 554 and solvolysis 452 cross coupling 553 with alkynes 945 relationship 383 crystallization 246 with allylic halides, solvent free guanidine-nitric acid 631 deprotonation 733 1129 guanidines, addition of ammonia dihalides 747 with amides 1158 to cyanamide 1126 dihalides, and elimination 747 with amino-ethers 570 and formation of aziridines dioxane and magnesium halide with aryl halides 553, 806, 524 245 1129 and supercritical ammonia 393 ether complex 246 benzyne mechanism 805 from amines 1126 Grignard reagents, formation, and Kumada coupling 807 guest–host complexes see CIDNP 748 with carbamates 588–589 complexes and radical ions 749 with carboxylic esters 1157 guest–host interactions, and a and radicals 748 with carbon dioxide 1160 carciplex 125 of aryl ketones 670 with dihydropyrans 570 and carcerands 125 Grignard reagents, from alcohols with epoxides 571 and molecular shape 122 568 with ethers 571 and urea 122–123 from alkyl halides 747 with formic acid 743 and water as host 124 from dihalides 747 with halogens 739 guests, and crown ethers 117 heat of formation 246 with hydrazones 1166 diesters 123 heteroaryl halides 1570 with imines 1162 in guest–host interactions 124 homocoupling 658 metal catalyzed 1163 ions in guest–host complexes in triethylamine 247 with iminium ions 568 119 initiators 747 with iron pentacarbonyl 743, p-iodoaniline 127 mechanism of formation 748 821 gyroscane 131–132 Grignard reagents, metal catalyzed with isocyanates 1168 gyrotops 131 addition to alkenes 946 with isocyanides 1265 addition to alkynes 946 with isonitriles 1169 H atoms, abstraction of by coupling 880–881 with ketones 1129 radicals 852 Grignard reagents, metal with lactams 570 rate of abstraction by radicals, exchange 554 with metal catalysts 553 and structure 852 Grignard reagents, Michael with methoxyamine 741 half-chair conformation, and addition with nitroalkenes, with nitriles 1168 cyclopentane 202 enantioselective 963 flow reactions 1168 half-life 461 with alkenes, mechanism 963 with nitrones 1167 and kinetics 301 Grignard reagents, Michael with ortho esters 570 definition 301 reaction 1159 with oxazines 591 of equatorial chair nitrogen containing 747 with oximes 1166 conformation 195 optically active 690 with phosphonic esters 567 radical 251 pinacol coupling 1134 with selenium 738 vinyl alcohol 99 powdered 747 with sulfonyl halides 1270 halide exchange 534 preparation 749 with sulfur 738 aryl halides 791 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2004 SUBJECT INDEX

halide ions, and phase transfer SN2 mechanism 1226 and the Arbuzov reaction 1198 535 tetrahedral mechanism 1227 and the E2 reaction 1311 Finkelstein reaction 534 with alkynes 598, 980 and the Hunsdiecker reaction with ditosylamines 543 metal catalyzed 1156 886 halides, acyl, and enamines 587 with amides 1248, 1313 and the Kornblum reaction, and Friedel-Crafts acylation with amines, and reagents 1490 661 Schotten-Baumann and the SN1 mechanism 378 and O-acylation 1252 procedure 1239 and Ullman reaction 559 and Rosenmund reduction 1549 with ammonia or amines 1239 and von Braun reaction 544 and Schotten-Baumann with boronic acids 1155 and water 483 procedure 1227 with carboxylic acid salts, anti-elimination 1278 and the tetrahedral mechanism formation of anhydrides halides, alkyl, base induced 452 1235 elimination 1311 aryl, conversion to ketones 670 with dialkylcadmium reagents mechanism 1312 carbonylation 670 670 carbonylation 605 condensation with nitriles 1236 with diazomethane 712, 1363 with alcohols to give esters conversion to diketones 1252 with DMF 1239 604 conversion to isocyanates 533 with hydrogen peroxide 503 with sodium coupling with boronic acids with hydrogen sulfide 1237 tetracarbonylferrate 604 804 with hydroxylamine-O-sulfonic catalytic hydrogenation 1568 decarbonylation 754 acid 1372 chiral, from chiral alcohols decarbonylation, mechanism with imides 1249 539 890 with metal catalyst 1315 halides, alkyl, conversion to exchange with carboxylic acids with organocuprates 1154 aldehydes 601 1251 with organometallic reagents to esters 605 from carbocyclic acids, 1155 to esters, metal catalyzed 605 reagents 1250 with thiols 1227, 1237 to isocyanates 533 from oxalyl halides and with urea 1249 to organolithium reagents carboxylic acids 1251 with water 1218 749–750 from trihalides and sulfur with ynones 1156 halides, alkyl, conversion to trioxide 484 halides, alkyl, addition to alkenes organometallics 750 halides, acyl, hydrogenolysis 1003 halides, alkyl, coupling of 1549 Friedel-Crafts catalysts 1004 Grignard reagents 550 hydrolysis 1218 metal catalyzed 1004 with boranes 593 and SN2 mechanism 1218 addition to alkynes 1003 with metals 549 halide reactivity 1218 alkylation and ultrasound 477 and radicals 563 mechanism 1218 amines and with boronic acids 801 reactivity order of halides hexamethylenetetramine halides, alkyl, dehalogenation 1218 514 1567 Lewis acid catalyzed addition to amino, with water 1367 dehalogenation, reagents 1566 alkenes 1005 halides, alkyl, and aniline 514 dihalides see dihalides metal catalyzed decarbonylation anti-elimination 1275 electrochemical carbonylation to alkenes 1315 and B strain 378 603 to ketenes 1320 and bond angle 27 enantiopure, and E2 reactions peroxides induced and carbanions 249 1275 decarbonylation 889 and carbocation formation 226 exchange with organolithium photochemistry 1252 and carbocations 412 reagents 237, 1134 reaction with alkenes 720 and Collman’s reagent 602 Finkelstein reaction 534 reactivity 1155 and E2 reactions 1274 formation of carbenes 270 reduction reagents 1549 and Friedel-Crafts alkylation formation of onium salts 358 reduction to alcohols 1580 648 formation of sulfonate esters reduction to aldehydes, and Grignard reagents 247 505 reagents 1549 and halide ions 534 halides, alkyl, from alcohols 423, Suzuki coupling 804 and hydroxides 483 536 halides, acyl, with active and I strain 379 from alkanes 856 methylene compounds and isonitriles 600 from alkenes with peroxides 1252 and lactams 477 1348 with active methylene and Menshutkin reaction 513 from alkyl halides 534 compounds 1252 and SET mechanism 1569 from alkyl sulfates 535 with alcohols 1226 and silver compounds 471 from amines 543 with alcohols and Zn 1227 and silver nitrate 471 from ammonium salts 544 metal catalysts 1227 and strain in carbocation from carboxylic acids 887, SN1 mechanism 1227 formation 378 1238 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2005

metal catalyzed 1238 to hydrocarbons, reagents with thiocyanate ion 512 reagents for 886 1566 with thiols 507 from cyanogen bromide 544 with cyanoborohydride 1568 with thiosulfate ion 510 from Grignard reagents 739 chemoselectivity 1568 with thiourea 506 from halogens 856 SN1 in sulfur dioxide 412 with tin sulfides 506 from mineral acids 537 solvent effects 1567 with trialkyltin hydride 1568 from organometallic reagents solvolysis and carbocations 306 with trimethylsilyl cyanide 600 739 and I strain 379 Wurtz coupling 549 from organometallics 739 and mechanism 357 halides, allylic, and Pd complexes from oxonium salts 541 steric hindrance and reactivity 44 from PPh3 and CCl4 and 377 Delepine´ reaction 515 alcohols 537 syn elimination 1278 formation with no from sliver carboxylates 886 trihalides see trihalides rearrangement 536 from sulfonate esters 535 halides, alkyl, with acetylide ion with anilines and hyponitrites from thionyl chloride 537 596 830 from tosylates, and microwaves with AgCN 481 with Grignard reagents, solvent 536 with aldehydes and amines free 1129 halides, alkyl, Gabriel synthesis 1120 with organolithium reagents 529 with amines or ammonia 513 552 halogen abstraction by radicals with aromatic compounds 648 with organometallics 559 851 with aryl organometallics 805 halides, amino, formation of cyclic homocoupling 559 with azides 531 amines 515 homolytic cleavage 844 with carboxylate salts 499 halides, and allylic rearrangement hydrodehalogenation 1568 with cyanide ion 480, 599 863 hydrolysis mechanism, SN1 with dianions 479 and carbamate formation 501 reaction 378 with dissolving metals 1568 and SN1 reactions 412 hydrolysis of 483 with disulfide ions 510 halides, aryl, acyl aniline ionization to carbocations 235 with enamines 587 derivatives 679 Katritzky pyrylium-pyridinium with enolate anions 370, 479 amination 636 method 543 with ethers 503 halides, aryl, and carbonylation Lewis acid catalyzed addition to with Grignard reagents, ESR with alcohols 821 alkenes 1003 554 and diboronic acid 738 alkyl halides to alkenes 1003 mechanism 553 and Friedel-Crafts alkylation mechanism of hydrolysis 483 with hydride reagents 1567, 648 meso, and E2 reactions 1275 1569 and Grignard reagents 1129 metal catalyzed carbonylation with hydroperoxide ions 503 and hyperconjugation 46 604 halides, alkyl, with lactams 529 and metal catalysts, Kumada coupling 562 with lithium 1134 coupling 807 metal mediated 550 with magnesium 747 and Orton rearrangement 679 carbonylation 603 with metal cyanides 600 and resonance 46 halides, alkyl, oxidation to with metals 1568 and SRN1 mechanism 774 aldehydes 1489 with nitrite ions 480 and Stork enamine reaction 587 to aldehydes, the Sommelet with nitrites 530 and the Heck reaction 811 reaction 1490 with nitro compounds 480 carbon dioxide, and metal with DMSO, mechanism 1490 with organocopperzinc catalyst 667 oxidative coupling with base reactants 558 carbon monoxide, aryl 1508 with organocuprates 555 iodonium compounds, and radical, conjugate addition 969 mechanism 555 metal catalyst 670 rate of hydrolysis, table 378 with organometallics 558–563 phenylboronic, and metal rates of solvolysis 379, 450 mechanism 559 catalyst 670 halides, alkyl, reaction with with organozinc compounds carbonylation with dicobalt alkoxides 490 559 octacarbonyl 821 with amines 517 with oximes 505, 1217 and metal catalysts 670 with aromatic compounds with phenoxide ions 480 conversion to aryl nitriles 793 648 with phosphines 1194, 1198 conversion to arylboron reactivity in carbonylation with phosphonates 590 compounds 792 reactions 604 with radicals 848 halides, aryl, coupling with reactivity with ethanol, table with RLi, radical intermediates arylmetallic, metal 377 253 catalyzed 808–809 reagents 1568 with silver compounds 503 with active methylene rearrangements and reduction with sulfinic acid salts 511 compounds 820 1568 with sulfonamide salts 530 with alkenes 811 reduction to alkanes 1568 with tetracarbonyl ferrate 602 with aromatic compounds 880 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2006 SUBJECT INDEX

halides, aryl, coupling with with hydroxide 779 from sulfonates 536 arylmetallic, metal with ketones, and from trialkylsilyl halides and catalyzed (Continued) N-heterocyclic carbenes alkenes 911 with boronic esters 804 819 from triflates 536 with enolate anions 820 with metal alkynes 816 halides, heteroaryl, conversion to with Grignard reagents 796 with metal halides 791 heteroaryl nitriles 795 with heteroaryls 796 with metaloalkynes, flow dehalogenation 1570 with trifluoroborates 804 reactions 816 Grignard reagents 1570 halides, aryl, dehalogenation 1569 halides, aryl, with metals 685 hydrogenation 1570 mechanism 1570 with nitrite salts 874 metal catalysts 1570 photochemical 1570 with organometallics 559, 685, halides, inorganic, with halides, aryl, from aromatic 1143 anhydrides 1251 sulfonyl halides 1590 with phosphines 790 with carboxylic esters 1251 from aryl halides 791 with potassium thiocyanate 784 halides, leaving groups, and from aryldiazonium salts 827 with silanes 1570 benzyne formation 773 from organometallic reagents with sulfur nucleophiles 937 magnesium, Grignard reagents 739 with thiolate ions 783 245 halide exchange, and with thiols, metal catalysts 783 metal see metal halides microwaves 791 solvent effects 783 and transmetalation 744 homocoupling 796 with vinylsilanes 546, 822 metal induced elimination to hydrodehalogenation 1570 halides, arylation of alkenes, metal alkenes 1318 hydroxylation 779 catalyzed 811 oxidation via the Krohnke¨ and microwaves 780 halides, benzoyl, solvolysis 125 reaction 1491 metal catalyzed carbonylation halides, benzylic or allylic, phosphorus, and 821 oxidation 1490 Hell-Volhard-Zelenskii coupling 562 Delepine´ reaction 515 reaction 708 photochemical coupling with from alcohols with microwaves primary, Friedel-Crafts aromatic compounds 879 478 alkylation 651 photochemistry 820 oxidation by the Kronke¨ SN1 reactions 471 reaction with amines 785 reaction 1491 halides, propargyl, and Glaser structural variation in oxidation with reaction 876 homocoupling 798 hexamethylenetetramine with aldehydes or ketones 1145 substitution by amines, base 1491 halides, reactivity as a function of catalysis 769 oxidative coupling to alkynes the halide 513 sulfonyl, conversion to aryl 1508 and hydrolysis of acyl halides halides 1590 oxidative coupling to tolanes 1218 thermal hydro-dehalogenation 1508 in benzyne formation 773 1571 solvolysis 455 in benzyne mechanism 773 via the Sandmeyer reaction 827 with halides 535 order, in acyl halide hydrolysis halides, aryl, with alkoxide, and halides, carbon tetrahalides and 1218 microwaves 781 complex formation 116 halides, selenyl 863 with alkoxides 781 carbonylation, and arylboronic silyl, with alkenes and DMSO SON2 mechanism 783 acids 822 1000 with alkoxysilanes 822 cyclic, and E2 reactions 1277 with allylsilanes 545 with alkynes, metal catalysts cyclohexyl, anti- or sulfenyl 999 950 syn-elimination 1278 halides, sulfonyl and the Reed with alkynyl trifluoroborates cyclopropyl 1358 reaction 872 819 and allylic carbocations 456 reduction to thiols 1590 with allylic esters 564 cyclopropylcarbinyl, and addition to alkenes or alkynes with amides 789 organocuprates 444 999 with amines 769 and SN2′ reactions 445 aromatic 641 with aryl organometallics 795 dialkylamino, fragmentation base induced elimination to with arylboronic acids 798 1321 sulfenes 1314 with CuCN 794 diarylmethyl 412 formation of sulfenes 1267 and microwaves 794 dihalides see dihalides from diazonium salts 785 and phase transfer agents electrochemical elimination to from hydrocarbons 872 794 alkenes 1318 from sulfonic acids 1270 in ionic liquids 794 from alcohols 538 halogenation of sulfonic acids with Grignard reagents 553, in ionic liquids 538 1269 806 from alkenes 989 hydrolysis 1267 Kumada coupling 807 from carbonates 536 with alcohols 504, 1268 with halide ions 791 from ethers 539 with alkenes 999 with hydrosulfide anion 783 from phosphates 536 with alkyl halides 511 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2007

with alkynes 999 by oxidation of alkenes 1500 haloammonium salts, heating with amines 1208, 1313 with tributyltin hydride 1359 1434 with ammonia or amines 1269 halo organolithium reagents 750 haloarenes 776 with arylboronic acids 1271 halo sulfides, Pummerer haloarenes, nucleophilic with Grignard reagents 1270 rearrangement of substitution and ultrasound with halo esters, Lewis acids sulfoxides 1603 333 catalysis 559 halo sulfones, and halocarbenes 269, 1068–1069 with organometallic reagents Ramberg-Backlund¨ and insertion 725 1270 reaction 1316 halocarbonyl compounds, halides, symmetric coupling 551 based induced elimination to coupling with alkenes 801 tertiary alkyl, elimination in the alkenes 1316 halochromates, phosphonium Stork enamine reaction halo-acetals, from vinyl ethers 1449 587 997 picolinium 1449 trialkylsilyl, and indirect halo-acids, from carboxylic acids tetraalkylammonium 1449 hydration 914 708 halocyclopropanes, flash vacuum with alkenes 911 Hell-Volhard-Zelenskii reaction pyrolysis 1358 with organocuprates 961 708 haloesters, and the Reformatsky halides, vinyl 708 lactone formation 286 reaction 1152 and addition–elimination 446 halo-alkenes, radical cyclization metal mediated addition to and elimination–addition 971 aldehydes or ketones 1152 reactions 449 halo-amines, by addition of from alkenes 996 and SN2 449 haloamines to alkenes halogenation, aldehydes, and SRN1 reactions 449 1000 enantioselectivity 704 and Stille coupling 717 formation of aziridines 515 alkenes, and Cinchona and substitution 446 formation of cyclic amines 515 alkaloids 994 and the element effect 446 halo-carboxylic acids 543 amino 1001 and the tetrahedral mechanism halo-ethers 1019 and acyl anilines 679 446 halo-ketones, addition of acyl and hydantoins 863 and thiol anions 446 halides to alkenes 1004 and hypochlorites 863 by addition of alkyl halides to Friedel-Crafts catalysts 1004 and peroxides 863 alkynes 1004 from ketones 704 and UV light 863 coupling with alkyl halo-lactams, from alkene–amides aniline derivatives 644 organometallics 719 1000 aromatic side chain 644 coupling with metals 560 from sulfonyl-amino-alkenes and ate complex of halogens from aldehydes or ketones with 1000 643 phosphorous pentachloride halo-nitro compounds, from arenium ions 643 1127 alkenes and nitryl chloride aryl, and Lewis acids 644 from alkynes 911–912 1001 carbonyl, and enols 706 and microwaves 912 halo-nitroso compounds, from halogenation, carboxylic acids from vinyl halides 534 alkenes 1001 708–709 from vinyliodonium halo-thioethers, from alkenes and and NBS 708 tetrafluoroborates 739 silyl halides 1000 and radicals 709 metathesis 1430 haloacylation of alkenes, and the halogenation, conjugated ketones oxymercuration 483 Vilsmeier reaction 1005 708 with Grignard reagents 553 haloalcohols see alcohols, halo electrophilic 857 with organometallics 559 haloalkenes see halides, vinyl formation of acyl chlorides 862 halides, with conjugated carbonyls haloalkylation 656 in water 992 1151 and Friedel-Crafts catalysts 656 ketones, enantioselective 707 Haller-Bauer reaction 759, 1249 haloalkynes, and metal catalyst metal mediated 861 mechanism 759 598 mixed 995 halo acetoxylation, of alkenes by electrolysis 740 halogenation, of alcohols 536 1025 metal mediated arylation 597 of alkanes 857 halo amides, and the Hofmann haloamidation 1001 and UV 857 rearrangement 1371 intramolecular 1001 fluorination 857 halo ammonium salts, cyclization haloamines 1371 See also amines mechanism 859 1433 addition to alkenes 1000 halogenation, of alkenes 894, 910 halo azides see azides conversion to methoxyamines and bridged ions 992 halo azides, with LiAlH4 1003 1378 and radicals 992 halo ethers see ethers from amines 763 and the Prins reaction 1004 from alcohols and halogens halo see haloamines enantioselectivity 994 997 reaction with acids 1433 halonium ions 992 halo ketones, and the Favorskii with acid 1434 iodosaccharin or rearrangement 1361 with radical 860 bromosaccharin 997 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2008 SUBJECT INDEX

halogenation, of alkenes with alcohols 997 and reactions that do not fit 381 (Continued) and alkenes 996 and reactivity 381 mechanism 992 halogens, with alkenes and sulfur field effects 381 radical mechanism 995 dioxide 872 resonance effects 381 and radicals 862 with aromatic compounds 642 Hammett reaction constant, and reagents 858 with boranes 740 acidity 372 selectivity 858 with Grignard reagents 739 Hammett relationships, and SNAr stereochemistry 994 with organometallics 739 reactions 777 with fluorine 994 with phosphites 1128 Hammett σ values, electrophilic halogenation, of alkynes 992, with silver carboxylates 886 aromatic substitution 627 995 with vinyl boranes 740 Hammett σρ-constants 903 sterochemistry 995 Halohydrin dehalogenase, Hammett σρ relationship, and of allenes 996 Arthrobacter sp. AD2 523 substituent effects 455 of arenes 862 halohydrins see alcohols, halo Hammett-Brown σ+ρ-relationship of aromatic compounds 642 halohydrins, dehydration 1300 627 of enolate anions 740 epoxide formation 424, 493 Hammond postulate 293, 614 of furan 645 from alkenes 996 and carbocations 450 of ketones, and microwaves mechanism 997 and transition states 450 704 from epoxides 541 definition 291 Cinchona alkaloid catalyst reagents, with alkenes 996 Handbook of Chemistry and 707 Williamson reaction 493 Physics 1620 Dess-Martin periodinane 708 haloketones, from diazo ketones Handbook of Naturally Occurring flow reactions 707 543 Compounds 1620 metal mediated 705 rearrangement to carboxylic Handbook of Organometallic reagents for 704 esters 1361 Compounds 1620 regioselectivity 706 halolactamization 998, 1000 handedness, and enantiomers 134 of lactams 765 reagents for 998 Hantzsch 1,4-dihydropyridines of silanes 862 halolactonization 998 1445 photolytic 847 gem-dimethyl effect 999 Hantzsch dihydropyridines, and propargyl 863 organocatalysts 999 aromatization 1444 of thiophene 645 and Markovnikov’s rule 999 and reductive alkylation 1119 halogenation, radical, allylic cobalt–salen complex 999 Hantzsch esters 559, 1555 hydrogen 862 enantioselectivity 999 amines, by reduction of amides mechanism 864 organocatalysts 999 1581 and AIBN 863 reagents for 998 and reduction 1528 and alkenes 862 Halomonas elongate, asymmetric hydrogen transfer benzylic hydrogen 862 transaminase 521 1544 bond dissociation energy 860 halonitroso compounds 1002 reduction of conjugated alkenes metal catalyzed 864 halonium ions 230, 466, 992–993 1527 halogenation, reactivity of HX neighboring group effects 425 reduction of imine-esters 1555 861 solvent effects 993 reduction of imines 1555 sulfoxides, reagents for 709 stabilization 994 reductive amination 1122 unsymmetrical ketones, stable 425 transfer hydrogenation, of regioselectivity 706 halonium radicals 847 imines 1554 Wohl-Ziegler reaction 857 halosilanes see silanes hapto complexes, of halogens, addition to alkenes 992 halosulfonation 641 cyclobutadiene 74 addition to alkenes, in ionic halosulfones see sulfones, halo hapto prefix, and metal complexes liquids 1001 halosulfonyl esters 999 114 addition to alkynes 992 halothiocyanates 999 hard acids, and HSAB principle and bridged ions 992 halotosylamine 1000 361 and haloform reaction 757 Hammet ρ-value, and transition and ionic bonds 361 and Lewis acids 643 states 1287 definition 359 and the Reed reaction 872 Hammett acidity function, and definition 359 cleavage of methyl ketones 757 solvents 352 hard and soft acids and bases mixed, alkenes 995 Hammett equation 385, 389 359–361 See also HSAB halogens, of ketones, and aromatic carboxylic acids table 360 enantioselectivity 705 381 hard bases, and ionic bonds 361 polarizability 643 and aromatic substitution 626 hardness 359 reaction with alkanes 857 and equilibrium constants 381 absolute 64, 359, 361 reaction with amides 1371 and linear free energy table 361 reactivity and halogenation 861 relationship 383 activation 625–626 reactivity in aromatic and radicals 853 and aromaticity 64 halogenation 642 and rate constants 381 and ionization potential 360 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2009

and Lewis acids 359 and high pressure 812 in ionic liquids 1185 and SN1 reactions 410 and microwaves 335, 812 metal catalyst 1186 model, and aromaticity 58 and N-heterocyclic carbenes organocatalysts 1186 Hartree-Fock calculations, and 275 solvent free 1185 annulenes 78 and neighboring group effects suitable bases 1185 Hartree-Fock method 36, 78 812 variations 1185 Hauptwerk (das Hauptwerk), of and palladium 811 heptahelicene, and chirality 145 Beilstein 1617–1618 arylation 812 and mechanical resolution 170 Haworth reaction, Friedel-Crafts base free 811 heptalene 67 acylation 660 biomimetic 814 and chirality 144 Hay reaction 876 enantioselective 812 derivatives, stability of 67 and the Glaser reaction 876 flow reactions 811 Herndon model 57 mechanism 877 in aqueous media 811 Hess-Schaad model 57 HBr, and hydrogen bonding 111 in ionic liquids 811 hetarynium ions 623 and peroxides, with alkenes in poly(ethylene glycol) 811 hetereoannulenes 79 910 in supercritical carbon dioxide hetereobimetallic catalysts 1516 and radicals, addition to alkenes 811 hetero-Diels-Alder reaction see 970 in supercritical water 811 heteroatom Diels-Alder cleavage of ethers 486, 540 intramolecular 812 reaction reaction with alcohols 423 ionic liquids 394 hetero[n]rotaxanes 131 with alcohols 537, 540 kinetics 813 heteroacenes 84 with alkenes 910 ligand free 811 heteroaromatic compounds 58 with cyclopropane 906 mechanism 812–813 amination 636 with dienes 898 metal catalysts 814–815 and aromaticity 58 with NBS 864 photochemical 812 aromaticity index 63 HBuIm, ionic liquids 394 reactivity of alkenes 814 with alkynes 949 HCl, and hydrogen bonding 111 regiochemistry 812 with diaryliodinium salts 658 as an acid 340 sila reaction 814 heteroaromatic coupling 658 cleavage of ethers 486 solid state 811 heteroaromatic, Friedel-Crafts reaction with acetate 340 vinyltrifluoroborates 815 alkylation 648 with alcohols 537 Heilbron’s Dictionary of Organic heteroaryls, coupling with aryl with alkenes 349, 910 Compounds 1619 halides 796 with crotylmercuric bromide helical chirality 144 See also coupling with arylboronic acids 695 chirality 801 HCN, addition to alkenes 991 helicenes 144 zinc reagents 561 addition to C=N compounds and a chiral axis 152 heteroatom Diels-Alder reactions 1212 and chirality 144 1051–1055 addition to HCN 991 helix, and chirality 144 dehydrogenative 1054 and cyanohydrins 980 Hell-Volhardt-Zelenskii reaction enantioselectivity 1053 and hydrogen bonding 110 147, 708 inverse electron demand 1054 and proton transfer 351 hemi-mercaptals, from aldehydes metal catalysts 1053 from cyanohydrins 991 or ketones 1108 solvent effects 1052 heat of atomization 29 hemiacetals 1103, 1381 structural variations 1054 and isomers 29 and acetal hydrolysis 486 with Lewis acid catalysts 1052 calculation 30 and formation of acetals 1102 heteroatom nucleophiles, of alkanes 29 conversion to ketones 1381 conjugate addition 975 of benzene 37 hydrolysis, reagents 1103 heteroatom stabilized of butadiene 41 stability 1103 carbocations 235 of ethane 29 hemiaminals, and formation of heteroatom vinylcyclopropane heat of combustion 29, 32 imines 1111 rearrangement 1407 and cycloalkanes, table 214 conversion to aminals 1113 heteroatom–hydrogen interactions annulenes 87 hemicarcerands, and carbenes 111 cis/trans isomers 178 269 heteroatoms, and acidity of heat of formation, Grignard and cyclobutadiene 73 α-protons 590 reagents 246 hemispherands 120 and catenanes 129 heat of hydrogenation 41 hemispheric 186 and crown ethers 119 for benzene 38 Henkel reaction 684 and hydrogen bonding 105 of cyclic alkenes 38 Henry reaction 1185 conjugated to carbanions 240 of cyclooctynes 216 aza- 1186 conjugation with carbocations heats of combustion 214 biocatalysts 1186 230 Heck reaction 308, 810 enantioselectivity 1186 2nd row, and the anomeric and ball milling 811 flow reactions 1186 effect 202 and boronic esters 737 gel-entrapped base 1185 in six-membered rings 199 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2010 SUBJECT INDEX

heterocycles, and Birch reduction heteropolytungstic acid 873 Hiyama coupling 546 1524 hexacarbonyldicobalt–alkyne enantioselective 546 and Friedel-Crafts alkylation complex 985 HMO theory, benzene 38 649 hexahelicene, and strain 220 and cyclopropenyl anion 75 and radical cyclization 975 hexahydro-Diels-Alder HMPA, and Brook rearrangement aromaticity 63 cycloisomerization 1043 1438 arylation 672 hexahydroazepin-2-one see and conjugate addition 980 by aromatization 1444 caprolactam and dialkylamide bases 369 by hydroamination, of alkynes hexaisopropylbenzene 219 and elimination 1312 928 hexamethlprismane 1063 and Grignard reagents 247 by reaction of aldehydes or hexamethyldisilazane, with enol and hydrogen bonds 108 ketones with amines 1113 ethers 721 and Normant reagents 951 carbonylation and formation of hexamethyldisilazide, with HOBr and HOCl, with alkenes ketones 822 tellurium salts 1207 996 carbonylation with alcohols with ammonium carboxylates Hoesch reaction 672 821 1242 and imino esters 672 catalytic hydrogenation 1524 with halo esters 1190 and the Gatterman reaction cyclopropanation 1073 hexamethylenetetramine, amine 672 cyclotrimerization, with metal alkylation 514 and thiocyanates 672 carbenes 1079 Delepine´ reaction 514 and thioesters 672 formation of thiocyanates 785 oxidation of benzylic halides mechanism 672 Friedel-Crafts acylation 660 1491 HOF, and explosions 997 metal reduction 1526 hexamethylphosphoramide see Hoffmann-Loffler-Freytag¨ SNAr reactions, flow reactions HMPA reaction see 770 hexaphenylethane 255 Hofmann-Loffler¨ reaction sulfur, reduction 1588 hexaphyrins 90 Hofmann degradation see with carbenes 1073 phosphonium adducts 89 Hofmann elimination N-heterocyclic carbenes 737 hexatriene–cyclohexadiene Hofmann elimination 1305 See also NHC interconversion 1394 and E2 mechanisms 1306 amides, by oxidation of HF, and hydrogen bonding 106, and Ei mechanism 1306 aldehydes 1498 111 and elimination 1290 catalysts 1150 cleavage of ethers 540 and Hofmann’s rule 1306 catalysts, benzoin fluorinating agent 535 and Sommelet-Hauser condensation 1216 with acyl halides 1251 rearrangement 835 catalysts, carboxylic esters, with alcohols 540 and Stevens rearrangement by oxidation of aldehydes with alkenes 910 1382 1496 with anhydrides 1251 and ylids 1306 catalysts, dehydrogenation with epoxides 540 and Zaitsev’s rule 1306 1249 high performance liquid mechanism 1306 catalysts, Grignard reaction chromatography see solvent effects 1306 1131 HPLC Hofmann exhaustive methylation Claisen rearrangement 1416 high pressure see pressure 1305 hydroacylation of high pressure mass spectrometry Hofmann rearrangement 1338, cyclopropanes 980 see mass spectrometry 1370 hydrocyanation 1211 high pressure, amines with esters and mechanism 293 umpolung of Michael 1246 mechanism 1370 acceptors 957 amines with lactams 1247 migratory aptitudes 1340 heterocyclic compounds 1626 and activation volume 390 of imides 1370 heterocyclic compounds, and Diels-Alder reactions 1041 reagents 1370–1371 alkylation 806 and rate enhancement 391 Hofmann-Loffler¨ reaction and tautomerism 103 and rate of diffusion 391 1433–1434 Knoevenagel reaction 1187 and reactivity 390 mechanism 1433 heterocyclic rings, by radical and transition states 390 Hofmann-Martius reaction 680 cyclization 973 Knoevenagel reaction 1187 Hofmann’s orientation, and heterodimer bases 368 higher order mixed organocuprate elimination 1290 heterofullerenes 91 556 Hofmann’s rule, and dehydration heterogeneous asymmetric highest occupied molecular orbital of alcohols 1299 catalysts 311 see HOMO and elimination 1289, 1292 heterogeneous catalysts 308 hindrance, steric see steric and Hofmann elimination 1306 and hydrogenation 1513 hindrance and sulfoxide elimination 1310 heterogenous, hydrogenation, Hinsberg test, and sulfonamides dehydrohalogenation 1312 mechanism 1517 1269 pyrolytic elimination 1298 heterolytic bond cleavage 280 hiscotropic rearrangement 1357 HOI, with alkenes 996 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2011

homoaldol reaction, and the homologous Mukaiyama aldol Huckel¨ molecular orbital Knoevenagel reaction reaction 1181 calculations 35 1189 HOMO-LUMO interactions, Huckel¨ system, and cyclobutene homoallylic alkenes 427 Diels-Alder reactions ring opening 1392 homoallylic carbocations 426 1045, 1052 cycloaddition reactions 1048 HOMO, allylic carbocations HOMO-LUMO overlap 1046 dienes 1393 1397 homolytic cleavage mechanism Huckel-M¨ obius¨ concept 88 and Diels-Alder reaction 1036 1304 rules for cycloaddition and symmetry of allylic cation hydrogen 1517 reactions 1048 1397 homolytic mechanism 280 Huckel’s¨ rule 73 and tetraenes 45 homo-metathesis 1429 and annulenes 77 ethylene 10 homooxacalixarenes 119 and aromaticity 71 of dienes 1393 [1,5]-homosigmatropic and aromaticity 76 overlap of orbitals in rearrangement 1419 Huisgen cycloaddition 1033 electrocyclic reactions homospheric 186 Hund’s rule, and aromaticity 71 1391 homotaurine, catalyst 1506 and photochemistry 316 homoanomeric interactions 200 homotropylium cations 65 and carbenes 267 homoaromatic compounds 90 HONO see nitrous acid Hunig’s¨ base, and aldol homoaromaticity 91 Hooke’s law, and molecular condensation 1174 and semibullvalene 1413 mechanics 204 and Claisen condensation 1253 heterocyclic compounds 91 Horner-Emmons see Hunsdiecker reaction 886 spherical 91 Horner-Wadsworth- and radicals 848 homoazulenes, and aromaticity 80 Emmons reaction and the Simonini reaction 886 X-ray 80 Horner-Wadsworth-Emmons catalytic 886 homo-Brook rearrangement 1437 reaction 1198 mechanism 887 homoconjugation 45 and phosphonate esters 1198 microwave irradiation 886 and carbocations 227 high pressure 1198 Hurtley reaction 819 cyclopropyl 46 horseradish peroxidase 1507 HX, with alkynes 894, 911 homocoupling, and dimethylzinc Hosomi-Sakurai reactions 967 anti-Markovnikov 911 562 See also Sakurai reaction hybridization 7 aryl halides 796 hosts, and crown ethers 117 and acidity 368 halides structural variation 798 crown ethers in guest–host and allenes 144 arylboronic acids 799 complexes 119 and aromaticity 51 copper catalyzed 797 cyclodextrins 127 and bond angle 27 Grignard reagents 658 water 125 and bond distance 26 of alkyl halides 559 water soluble 121 and bond energy 30–32 Ullmann reaction 797 hot spot, sonochemistry 332 and bond rotation 188 homocubene 221 Houben-Hoesch reaction see and boron 8 homocubyl radicals 1347 Hoesch reaction and carbanion stability 241 homodesmotic reactions 39 Houben-Weyl’s Methoden der and carbanions 242 homo-Diels-Alder reactions 1042 Organischen Chemie 1625 and conformations 188 homodienyl [1,5]-sigmatropic HPLC, and annulenes 89 and cyclophanes 50 hydrogen shift 1419 and enantiomeric catenanes and inductive and field effects homodienyl [1,5]-shifts 1404 130 22 homodimerization, of alkanes 875 and enantiomeric purity 175 and mercuric chloride 8 homoenolate ion 242 diastereomer separation 175 and PES spectra 15 homofullerene 92 HSAB principle 359–361 and prismane 212 homofullerenes 92 alkoxide bases 362 and pyrenophane 50 homogeneous catalysts 308, 1513 and carbonyl carbon 463 and radicals 258 hydrogenation, mechanism and enolate anions 361 and resonance energy 41 1518 and equilibrium 361 and SN2 reactions 404 homogeneous hydrogenation, and polarizability 480 hybridization, butadiene 41 catalysts, optically active and substitution reactions 480 diagonal 8 1529 electrophilic aromatic in ethyne 11 of conjugated alkenes 1529 substitution 625 of carbon 9 homogeneous reactions, and metal ions 361 of dienes 41 kinetics 297 table of acids and bases 360 of radicals 258 homogenous catalysts, and Huang-Minlon modification, and sp 11 hydrogenation 1513 microwaves 1577 trigonal 8 types 1514 of Wolff-Kishner reduction hybrid orbitals 9 homologation, addition to 1577 hybrid orbitals, sp 8 aldehydes or ketones 1365 Huckel¨ aromaticity 88 hybrid orbitals, sp2 9 by carbene insertion 725 rule 1045 hybrid orbitals, sp3 9 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2012 SUBJECT INDEX

hydantoin derivatives, with nitrous acid 761, 1371 and the Shapiro reaction photoisomerization 329 with propargylic alcohols 701 1308 hydantoins, and alkene hydrazobenzenes, acid catalyzed base induced elimination halogenation 997 rearrangement 1422 1308 and halogenation 863 by reduction of nitro conversion to acrylic acids hydrates, and equilibrium 1095 compounds 1561 1161 from aldehydes and ketones from aromatic nitro compounds suitable bases for elimination 1095 1560 1309 hydratases, nitrile, hydrolysis of from azobenzenes 1555 with organolithium reagents nitriles 1100 hydrazo compounds see 1309 hydration, alkynes, and metal hydrazines, aryl or diaryl with acid 164 catalysts 915 hydrazo compounds, by reduction with Grignard reagents 1166 anti-Markovnikov 913 of nitro compounds 1600 with ketenes 1262 differential see differential reduction to amines 1592 with Lewis acids 1419 hydration hydrazoic acid 517 hydrazyl radicals 256 indirect 914 addition to Michael-type hydride ions, and reduction 1441 mercuric catalyzed hydration of alkenes 931 from alkanes 698 alkynes, mechanism 916 and nitrile formation 1117 hydride reagents 1533 of aldehydes and ketones and the Schmidt reaction 1117, alcohols 1571 1095 1373 and reduction of amides 1581 acid or base catalyzed 1096 with alcohols and alkenes 1374 and reduction of nitriles 1558 of alkenes 912 with ketones 1373 carboxylic esters 1548 metal catalyzed 913 hydrazones, addition of HCN chemoselectivity 1533 of alkynes 914 1212 desulfurization 1588 anti-Markovnikov catalysts alkylation 585 reactivity 1533 915 and the Fischer indole synthesis hydride reagents, reduction of metal catalyzed 914 1419 alkyl halides 1567 of conjugated dienes 914 as derivatives 1115 of amides to aldehydes 1552 of vinylidene nitriles, and aziridino, LDA induced of amine oxides 1586 cleavage 913 elimination to cis alkenes of azo compounds 1592 hydrazide, acyl 552 1309 of azoxy compounds 1586 hydrazides 509 chiral 164, 1125 of carboxylic acids 1546 from esters 1247 conversion to alkenes 1308 of carboxylic acids, selectivity with nitrous acid 1371 conversion to diazo compounds 1547 hydrazine carboxylate, methyl 712 of nitriles, metal catalysts ester 109 [3+2]-cycloaddition 1028 1556 hydrazines, acyl see hydrazides epoxy, Eschenmoser-Tanabe of nitro compounds hydrazines, and hydrogenation of ring cleavage 1324 1559–1600 alkenes 1521 Fischer indole synthesis 1419 with acetals or ketals 1574 and reduction of aldehydes or from active methylene with alkyl halides 1569 ketones 1577 compounds 710 with amides 1552 and the osazone test 1116 from aldehydes or ketones with boronic acids, reduction of and Wolff-Kishner reduction 1419 carboxylic acids 1577 from aryldiazonium salts 710 1546–1547 aryl, amination 637 from carboxylic acids 710 with chiral additives 1544 aryl, amination, flow reactions from hydrazines and aldehydes with hydroperoxides 1576 637 or ketones 1115–1116 with ortho esters 1574 aryl, loss of nitrogen 1462 from oximes 1115 with sulfonate esters 1575 by Hofmann rearrangement hydrazones, hydrolysis 1097 with Weinreb amides 1552 with ureas 1370 Japp-Klingemann reaction 711 hydride rearrangements 1344 chiral 164, 1555 oxidation, to diazo compounds hydride reduction, aldehydes, diaryl, reagents for oxidation 1462 mechanism 1535 1462 to nitriles 1462 and microwaves 1533 in a complex 124 reagents 1462 and steric hindrance 1534 phenyl see phenylhydrazine reagents for hydrolysis 1098 carbonyls, substrate variations aldehydes or ketones 1115 reduction to amines 1553, 1563 1533 with aldehydes or ketones 1116 mechanism 1578 ketones, mechanism 1535 and pH 1115 reagents 1555 reduction of conjugated alkenes ball milling 1116 tosyl, and isotope labeling 1309 1527 rate of reaction 1115 and Knoevenagel reaction solvent effects 1533 with alkenes 927 1189 1,3-hydride shifts, and greater with alkynes 928 and the Bamford-Stevens 1344 with hydroxylamine 1239 reaction 1309 apparent 1344 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2013

hydride shifts 1434 (DHQ)PHAL 1021 bond energy 30 carbocations, energetics 1351 intramolecular 926 bowl-shaped 92 stability 1351 allene–amines 928 hydrocarbons, by coupling of transannular 1434 metal catalyzed 926 organocuprates 882 hydride transfer, and metal catalysts 929 by deamination of amines 1580 oxidation–reduction 1441 of alkenes 924 reagents 1585 and the Cannizzaro reaction mechanism 925 by decarboxylation 751 1602 enantioselectivity 1020 by dehalogenation of alkyl hydride, lithium aluminum, and metal catalyzed 1020 halides, reagents 1566 reduction of acyl halides of alkynes, formation of by desilylation of silanes 1566 1580 heterocycles 928 by hydrogenation of thiophenes and reduction of imines 1553 of dienes 928 884 reduction of azides 1564 organolanthanide catalysts by metal catalyzed reduction of conjugated 1021 decarbonylation of carbonyls 1533 hydroarylation, conjugated alkynyl aldehydes 888 reduction of imidazoles to ketones 950 by reduction of aldehydes aldehydes 1552 of alkynes 947 1577 reduction of iodoazides 1003 hydroboration 735, 932–937 of alkyl halides, reagents reduction of oximes 1562 and ate complexes 736 1566 with chiral additives 1544 and enantioselective synthesis of amines, reagents 1584 with epoxides 1441 935 of carboxylic acids 1583 with Lewis acids, reduction of and ether solvents 933 of diazonium salts 1587 ethers 1579 and flow reactions 933 of ketones 1577 hydride, tin 333 and hydration of alkenes 913 of nitriles 1583 hydride, tributyltin, reduction of and hydroxylamine O-sulfonic of silanes 1566 aldehydes 1540 acid 928 of sulfones or sulfoxides, and phenylboronic acid 1540 and NMR 933 reagents 1588 with radicals 843 and reduction of alkenes 1521 of thioethers, reagents 1588 hydrides, complex with carbonyls of alkynes to alkenes 1522 of thiols, reagents 1588 1536 and steric hindrance 933 hydrocarbons, CH amination hydrides, metal see metal anti-Markovnikov alcohols 1487 hydrides 1385 oxidation to amines 1486 hydrides, metal 1534 orientation 740 Hydrocarbons, conversion to reduction of boranes 1387 enantioselective 935 esters 1477 hydrides, and carbocation preparation of alcohols 935 with dialkyloxiranes 1477 formation 226 enantioselectivity 934 hydrocarbons, coupling of reduction of aldehydes or formation of unsymmetrical organometallics 882 ketones 1532 ketones 1387 hydrocarbons, from alkyl halides of epoxides 1531 mechanism 933 1569 of ketones, and Cram’s rule of alkenes 1521 from ammonium salts 1585 1546 anti-Markovnikov addition from arylhydrazines 1462 tin, reduction of aldehydes or 913 from azo compounds 1462 ketones 1540 mechanism 736 from Grignard reagents 1569 tri-tert-butoxy, lithium migration 700 from nitriles 1584 reduction of acyl halides to then aminating agents 928 from nitro compounds 1585 aldehydes 1549 of alkynes 740, 936 from phosphonium salts 1585 hydro-de-benzoylation 683 of enynes 737 from sulfides 1589 hydro-dehalogenation, thermal, preparation of from sulfoxides or sulfones aryl halides 1571 organomagnesium 1589 hydroacylation 980 compounds 548 from thiols 1589 alkynes 980 radical mechanism 740 hydrocarbons, halosulfonation allenes 980 rearrangement 736 872 cyclic ketenes 979 regioselectivity 933 hydroxylation 1476 cyclopropanes, and NHC 980 stereochemistry 905 enantioselectivity 1476 hydroalkylation, of alkynes 948 with conjugated dienes 936 enzymatic 1476 hydroamidation, of alkynes, in with metal catalysts 936 metal catalyzed coupling of supercritical CO2 931 hydrobromic acid see HBr Grignard reagents 880 of alkynes, ionic liquid catalyst hydrocarbons, acidity 238 hydrocarbons, oxidation 1476 931 alternant and non-alternant 68 to alcohols 1475 hydroamination, and radicals 929 and chirality 147 reagents 1476 cyclization 926 and guest–host interactions to hydroperoxides 867 and near-IR luminescence 123 to peroxides 870 926 and the Kolbe reaction 885 system 1477 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2014 SUBJECT INDEX

hydrocarbons, oxygen insertion and carbenes, mechanism 727 hydrogen bonds, and acceptor 1477 by radicals 846 basicity 107 mechanism 1477 π-allyl complex 700 and amides 107 reagents 1477 hydrogen, as an electrophile 629 and aqueous acetone 108 hydrocarbons, radical coupling of hydrogen atoms, abstraction 326, and dicarboxylic acids 107 carboxylate salts 885 330 and enol stabilization 701 reagents, for oxidation to and oxidation or reduction and guest–host interactions 121 alcohols 1476 1439 and heteroatoms 107 with acylperoxides 870 and the Schrodinger¨ equation 4 and neutron diffraction 108 with halogen and sulfur dioxide and wave functions 4 and ring size 108 872 shifts, transannular 1349 and semirubin 112 with hydroperoxides 870 transannular shifts 1348 and steric hindrance 111 with oxygen 867 transfer 973 and symmetry 109 with sulfur dichloride 872 transfer, and and water 107 hydrocarboxylation 982 oxidation–reduction 1441 and X-ray crystallography 108 acid catalyzed 984 hydrogen bond, bifurcated 108 hydrogen bonds, asymmetric 109 and carbon monoxide 982 distance 109 cooperative 109 and Markovnikov’s rule 984 malonaldehyde enol 108 crown ethers 121 and nickel carbonyl 984 nine-membered 108 enols 108 and the Koch reaction 982 radii 109 fingerprint 110 Markovnikov’s rule 983 hydrogen bonding 105–112 geometry 108 mechanism 983 acidity 106, 366 in crystal structures 112 metal catalyzed, mechanism and alcohol–alkynes 112 in the solid state 109 984 and alkynes 110 intramolecular 106 of alkenes 984 and amides 112 ionic 107 anti-Markovnikov 984 and aprotic solvents 110 lifetime 106 of alkynes 982–984 and boiling point 110 nonclassical 107 hydrochloric acid see HCl and bond energy 31 strong 106 hydrocyanation 1210 and chemical properties 110 three-center 108 enantioselectivity 1210–1211 and coupling constants 110 topology 107 N-heterocyclic carbenes and cyclopropanes 111 unconventional 106 catalyst 1211 and deuterium 112 with hydrogen halides 111 of alkenes 991 and dipyrrinones 112 hydrogen clathrate hydrates 123 selectivity 1211 and enol content 98 hydrogen epoxide, and base, hydrocyanic acid see HCN and HCN 110 epoxidation, conjugated hydrodehalogenation 1568 and IR 109, 112 carbonyls 1015 hydrodehalogenation, aryl halides and isocyanides 111 hydrogen exchange, and 1570 and melting point 110 cyclopropenyl derivatives hydroformylation, and aldol and molecular recognition 121 75 condensation 989 and NMR 108–109, 111 coupling of alkanes 724 and dicobalt octacarbonyl 990 and pK 366 electrophilic aromatic and polymerization 989 and polar solvents 470 substitution 629 and the aldol reaction 989 and proton transfer 350 mechanism 697 and the Tishchenko reaction and radicals 256 reactivity and structure 697 989 and Raman 109 with carbocations 724 cyclization 990 and solubility 110 hydrogen gas reducing agent 1120 enantioselective 990 and the ideal gas 110 hydrogen peroxide, and flow reactions 989 hydrogen bonding, aqueous Baeyer-Villiger formic acid catalyzed, of acetone 108 rearrangement 1378 alkenes 989 C—H 110 and hydroxide, with boranes metal catalyzed 989 carboxylic acids 106 1385 of alkynes 990 complex 350, 356 and hydroxylation of aromatic oxo process 989 cooperative 108–109 compounds 865 of alkenes 989 intermolecular 107 and oxidation of alcohols 1455 in supercritical carbon intramolecular 108, 351 and oxidation of amines to dioxide 989 neutron diffraction 113 amine oxides 1504 of alkynes 990 NMR and IR 109 and oxidation of thiols 1505, metal catalyzed 990 S-H 111 1509 stereoselectivity 990 solvents 106 with alkenes 1380 hydroformylation, retro 989 spectroscopic detection 109 with boranes 1385 stereoselectivity 990 strong 110 with carboxylic acids and DCC hydrogen abstraction, and weak 110–111 503 carbenes 727 with fluorine 111 [1,3]-hydrogen shifts 1403 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2015

[1,5]-hydrogen shifts 1403 and radicals 1517 of benzylic ethers 540 hydrogen shifts, and carbene and reduction of imines 1554 of carbonyls, mechanism 1537 rearrangements 1349 and Rosenmund reduction 1549 of cyclopropanes 1530 [1,5]-, with vinyl aziridines and selectivity 1519 of dienes 1516 1403 and stereochemistry 1519 of disulfides 884 [1,7]-antarafacial migrations and steric effects 1517 of heptalene 67 1403 and sulfur compounds 884 of heterocycles, [1,7]-, photochemical 1403 and Wilkinson’s catalyst 1513 enantioselectivity 1524 hydrogen sulfide clathrate 123 mechanism 1518 of imines, metal catalyst 1554 addition to alkenes 922 hydrogenation, catalytic, of iminium salts, metal catalyst clathrate 123 apparatus 1514 1554 leaving group 1126 hydrogenation, catalytic, aromatic of isocyanates 1556 with acyl halides 1237 compounds, of isothiocyanates 1556 with carbonyls 1107 enantioselectivity 1524 of lactones 1548 with ketones 1107 in supercritical ethane 1523 of nitriles 1557 hydrogen transfer reactions 843 ionic liquids 1523 of nitro compounds 1566 radical cyclization 972 phase transfer catalysts 1523 of oximes 1555 asymmetric, metal catalysts reactivity 1524 of phenols 1572 1544 hydrogenation, catalytic, of thioethers 883 chiral 1543 asymmetric catalyst 1543 of thiols 883 [1,4]-, in radical cyclization catalyst types 1513 of thiophenes 884, 1588 1403 chiral ligands 1515 hydrogenation, catalytic, pressure radicals and tributyltin hydride enantioselectivity 1515 1514 843 flow reactions 1197 reaction conditions 1514 and alkylsilanes 843 functional group compatibility reduction, of conjugated reduction of aldehydes or 1514 alkenes 1526 ketones 1541 heat of, for benzene 38 of nitriles, metal catalysts hydrogen–alkane exchange 1519 heteroaryl halides 1570 1556 hydrogen-bond basicity 347 metal catalysts 1570 Rosenmund catalyst 1516 hydrogen–deuterium exchange hydrogenation, catalytic, Rosenmund catalyst, and 697 heterogeneous, mechanism alkynes 1516 hydrogen–heteroatom interactions 1517 selectivity with homogeneous 111 homogeneous catalysts 1513 catalysts 1515 hydrogen–lithium exchange 806 mechanism 1518 soluble catalysts 1513 hydrogen-transfer agent, and of conjugated alkenes 1529 solvent effects 1516 radicals 970 ionic liquids 1514–1515 surface phenomena of metals hydrogen–tritium exchange 697 ligands 1514 1517 hydrogen, as a leaving group 675 for enantioselectivity 1515 types of homogeneous catalysts as a neighboring group 439 Lindlar catalyst 1516 1514 canonical forms 6 and alkynes 1516 hydrogenation, transfer see homolytic cleavage 1517 low pressure, carboxylic esters transfer hydrogenation migrating group in 1548 hydrogenolysis, alcohols 1571 rearrangements 1339 hydrogenation, catalytic, metal and aldehydes or ketones 1577 participation solvolysis 439 catalysts 1513, 1515 cleavage of ethers 540 sigmatropic migration in and aromatization 1443 hydroxy–amine intermediate alkenes or dienes 1400 hydrogenation, catalytic, of 1119 with amines and aldehydes or aldehydes or ketones 1536 hydroxy–amines 1119 ketones 1118 mechanism 1536 of acyl halides 1549 hydrogenase, reductive amination metal catalyst 1536 of alkanes 1444 1120 hydrogenation, catalytic, of of amines 1584 hydrogenation, catalytic 1513 alkenes 44, 1513 of esters 1575 See also transfer versus alkynes 1516 and the Barton-McCombie hydrogenation selectivity 1515 reaction 1576 and acyl halides 1550 with hydrazine 1521 reagents 1576 and biooxidation 1455 hydrogenation, catalytic, of alkyl of ethers 1573 and carboxylic esters 1548 halides 1568 of nitriles 1584 and chiral catalysts 165 of alkynes 1516 of sulfonate esters 1575 and cleavage of alkanes 759 metal catalysts 1516 hydrolysis, acid catalyzed 383 and D2 1519 selectivity 1516 and isotopes 1225 and enantioselectivity 1514 of allenes 902, 1517 and conformational mobility and metal catalysts 1454 of amides 1582 487 and phase transfer 1455 metal catalysts 1583 and stereoelectronic control and poisoning 1513 of aromatic compounds 1523 487 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2016 SUBJECT INDEX

hydrolysis, acid catalyzed hydrolysis, of esters, and malonic hydromethylation, of alkenes 948 (Continued) esters synthesis 577 hydroperoxide ions, with alkyl and the Gabriel synthesis 530 catalysis 1219 halides 503 and the Reformatsky reaction enzymatic 1220 hydroperoxide radicals, bond 1153 gas phase 1220 dissociation energy 258 base catalyzed 383 lipase 1220 hydroperoxides 503, 840 hydrolysis, of acetals 486 mechanism 296, 1220–1223 acid catalyzed rearrangement to and SN1 mechanism 486 microwaves 1220 ketones 1381 A1 and A2 mechanisms 487 phase transfer 1220 acyl, from anhydrides 503 acid catalysis 486 rate constants 384 and epoxidation 1017 and Brønsted coefficient rates 379 and singlet oxygen 869 487 structural variations 1220 by autoxidation 867 and hemiacetals 486 ultrasound 1220 cleavage 1576 and isotope labeling 486 hydrolysis, of ethers 494 from alkyl halides 503 rate determining step 487 of hemiacetals, reagents 1103 from carboxylic acids 503 of alkyl halides 483 of hydrazones 1097 from Grignard reagents and rate, table 378 reagents for 1098 oxygen 734 rates 379 of hydroxamic acid 1099 oxidation of silanes 499 SN1 378 of imines 1097 ozonolysis intermediate of amides 1224 hydrolysis, of iminium ions 1098 1468–1469 base-catalyzed reaction and Stork enamine reaction protonated 1381 1225 1098 reduction with P(OEt)3 1576 DNA hydrolysis 1226 mechanism 1098 tert-butyl, and dihydroxylation flow reactions 1224 hydrolysis, of iminium salts 672 of alkenes 1006 mechanism 1225 of inorganic esters 485 with hydride reagents 1576 reagents 1224 of isocyanates 1105 hydrophanous acids, with alkenes, tetrahedral intermediate of isothiocyanates 1105 mechanism 997 1225 of ketenes 1364 hydrophobic acceleration, in water of anhydrides 1218 of nitriles 600, 1099 391 nucleophilic catalysis 1218 and ionic liquids 1100 hydrophosphinylation, of alkynes hydrolysis, of aryl Grignard and microwaves 1100 931 reagents 686 flow reactions 1100 hydroquinones, and cathecols, of aryl organolithium reagents reagents for 1100 oxidation to quinone 686 with nitrilases 1100 1459 of aryl organometallics 686 with nitrile hydratases 1100 oxidation with Fremy’s salt of aryl oximes 836 with Rhodococcus 1459 of benzamide 1093 erythropolis SET1 1100 oxidation with Oxone 1459 of Bunte salts 506 hydrolysis, of nitro compounds oxidation with periodate 1459 of C=N compounds 1096 1098 oxidation, mechanism 1460 reagents for 1097 and the Nef reaction 1098 oxidation, reagents 1459 hydrolysis, of carbamates, reagents for 1099 hydroquinones, from quinones mechanism 1224 hydrolysis, of organometallic 1534 of carboxylic acid esters, and compounds 686 host for clathrates 124 mechanism 384 ortho esters 487 hydrosilanes, with nitriles 1584 of carboxylic esters 1219 of oxetanes 490 hydrosilation 940 of chloroform 484 of oximes 830, 1097 allenes 942 of compounds, and microwaves of phthalamic acid 1093 amines, from nitro compounds 1097 of phthalimides 530 1561 mechanism 1098 of Schiff bases 1097 of alkenes 940 of cyanide 295 of semicarbazones 1097 of alkenes, enantioselectivity of cyanohydrins 1100 of sulfinates 485 941 of diazoketones 485 of sulfonamides 1267 of conjugated alkenes, and of dihalides 484 of sulfonic acid derivatives metal catalysts 1528 of dithianes 589 1267 of conjugated alkenes, of dithioketals, and of sulfonic acid esters 485 enantioselectivity 1528 dithioacetals, reagents for of thiocyanates 1101 of imines 1553 1110 of trihalides 484 of imines, microwaves 1554 Corey-Seebach procedure RAMP or DAMP 1097 hydrostannation 333 1110 rate constants 383 and sonochemistry 333 of enamines, mechanism 1098 hydrometallation 937 hydrosulfide anion, with aryl of enol ethers 486, 488 of alkenes 937 halides 783 of epoxides 489 of alkynes 938 hydrothiolation, of alkenes 923 enantioselectivity 489 of arynes 939 with diynes 923 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2017

hydroxamic acids, from esters hydroxyamic acids, conversion to hydroxylmines, from isonitriles 1247 pyrrolidines 1359 527 from hydrazine and bis-, chiral 1017 hydroxynitriles 585 hydroxylamine 1239 from alkenes 1019 hydroxypropanoic acid, proton hydrolysis, mechanism 1099 hydroxybenzotriazole 1246 transfer 351 O-acyl, and Lossen hydroxybenzyl silanes, Brook hydroxypyridine, and tautomerism rearrangement 1372 rearrangement 1437 101 O-acyl, base catalyzed hydroxyl-silanes, for lithio-silanes N-hydroxysuccinimide see NHS rearrangement 1372 and aldehydes or ketones hydroxysulfenylation, of alkenes torsional barrier 194 1191 1018 hydroxide ion, and alkyl halides hydroxylactams, from lactams hydroxysulfinamides, by 483 1486 Knoevenagel reaction reaction with amides 377 hydroxylamines 1371 1188 reaction with silanes 239 by Meisenheimer hydroxytetrahydrofuran, from with aryl halides 779 rearrangement 1383 tetrahydrofuran 1484 hydroxy acids, and zwitterionic by oxidation of amines with hydrozirconation 1024 intermediates 1323 Caro’s acid 1502 of alkenes 938 by rearrangement of diketones by oxidation of amines, hyperconjugation 44, 92 1361 enzymes 1503 and alkene addition 906 elimination to alkenes 1323 by oxidation of amines, reagents and alkynes 94 from epoxy ketones 1362 for 1502 and aromaticity 94 ring closure to lactones 1602 by reduction of nitro and bond dissociation energy hydroxy aldehydes and ketones, compounds 1561 94 α-, conversion to osazones by reduction of nitro and bond distance 49, 94 1116 compounds, reagents 1561 and bond elongation 95 hydroxy amides, from addition of from amine N-oxides 1561 and canonical forms 49 amides to aldehydes from aromatic nitro compounds and carbanions stability 241 1122 1560 and carbocations 94, 226–227, hydroxy amines see amino ionic liquids 1115 233–234, 306, 452 alcohols metal reduction to amines 1561 and charge separation 95 hydroxy esters, by oxidation 1503 and conjugative stabilization α-hydroxylation 1483 reaction with aldehydes and 41 mechanism 1484 formic acid 1117 and cyclopentadienes 96 hydroxy ethers 497 reduction with carbon disulfide and delocalization 94 from epoxides 496 1562 and diynes 42 oxidation to acetals 866 with aldehydes or ketones, and and elimination 1289 hydroxy halides see halohydrins pH 1115 and isotopic effects 306 hydroxy ketones 1172, 1189 rate of reaction 1115 and MM4 calculations 95 by oxidation of alkenes 1500 with alkenes 927 and orbitals 94 by the benzoin condensation with formic acid and aldehydes and p character 94 1215 1117 and propene 95 by α-hydroxylation 1483 with HONO 1357 and quantum mechanics 94 mechanism 1484 with hydrazine 1239 hyperconjugation, and radicals by α-ketols rearrangement with organometallics 741 94, 254–255 1360 α-hydroxylation, of carbonyl and resonance 95, 226 from aldehydes and potassium compounds, reagents 1483 and ring strain energy 96 cyanide 1215 hydroxylation, aromatic and s character 95 from epoxy ketones 1532 compounds, Boyland-Sims and solvolysis 306 from metalated imines 1266 oxidation 674 and sp2 hybrids 94 hydroxy thiols, from carbonyls Elbs reaction 674 and tautomers 96 1107 potassium persulfate 674 and temperature 306 hydroxy–aldehydes 1172 hydroxylation, of alkenes 912 and the anomeric effect 201 hydroxy–alkyl halides see of alkyl, with organocatalysts and the Baker-Nathan effect halohydrins 1477 93–94 hydroxy–amine intermediate, of aromatic compounds, and and the tetrahedral mechanism hydrogenolysis 1119 Lewis acids 674 447 hydroxyalkylation, and aluminum of hydrocarbons, and UV 92 complexes 653 enantioselectivity 1476 and X-ray analysis 94 and ketones 653 enzymatic 1476 aryl halides 46 aromatic compounds, of silanes 498 isovalent 94 atropisomerism 653 of tetrahydrofuran 1484 negative 96, 201 boron reagents 653 photolytic 675 radicals 261 Lederer-Manasse reaction 653 with aniline derivatives 674 sacrificial 96 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2018 SUBJECT INDEX

hyperconjugative stabilization 94 imidazolinyl carbene ligand, reagents 1563 stretching 95 chiral 1143 carbonylation 988 hypervalent iodine 500 See also Imidazolium carbocations imines, conversion to amides iodine 230 1435 and dihydroxylation 1008 imidazolium catalysts 1054 to nitriles 1461 aromatic fluorination 647 imidazolium salts, ionic liquids to β-lactams 1057 catalyst 311 393 imines, cyclic, from cycloalkyl reagents 508 imides, acyl, intermediate in azides 1372 and ionic liquids 1454 McFadyen Stevens from tetrahydroisoquinolines selenium dioxide, α-oxidation reduction 1552 1446 of ketones 1487 alkyl 519 via radical cyclization 1217 with alkenes 997 by carboxylation of alkenes imines, [2+2]-cycloaddition with alkynes 597 988 1058 with aromatic compounds 646 cyclic 1241 cyclohexanone, aerobic hypobromites 998 amines and cyclic anhydrides dehydrogenative hypochlorites 998 1241 aromatization 1444 alkyl, and radicals 841 formation, anhydrides with electronic structure 17 decomposition to radicals amines 1241 ene reaction 953 841 from acyl halides and amides enzymatic reduction 1553, and aminohydroxylation 1020 1249 1555 and epoxidation 1017 from amides 1487–1488 E/Z-isomers 218 and halogenation 863 and Selectfluor 1488 from alkyl azides 1372 and radical halogenation of Hofmann rearrangement 1370 from amines 1461 silanes 862 reduction to amines 1583 and aldehydes 1111 sodium, with amines 763 imidines, from dinitriles 1126 and ammonia 1119 with azides and aldehydes 1250 imido selenium compounds, with and ketones 1111 hypofluorite, acyl, with enolate alkenes 713 by dehydrogenation 1445 anions 706 imido sulfur compounds, with metal catalyzed 1461 hypohalides, and N-haloamines alkenes 713 imines, from azides 1372 763 imidodiphosphate catalyst, from aziridines 1461 hypohalites, acyl, as an confined 954 from enol ethers 1124 intermediate 887 imidodiphosphoric acid catalyst from nitroso compounds 711 hypohalous acids 996 656 Hantzch ester transfer addition to alkynes 997 imidoyl radicals 842 hydrogenation 1554 with alkenes 996 imine-enamine tautomerism see hydrogenation, metal catalysts with alkynes 997 tautomerism 1554 hypoiodites 998 imine-esters, and Hantzsch esters hydrolysis 1097 hyponitrites, and addition to 1555 to aldehydes or ketones 1491 alkenes 981 imines, acylcyanation 1213 hydrosilation 1553 hypophosphorus acid, and addition of carbenes 272 microwaves 1554 reduction of aryldiazonium addition of diazoacetates 1022 in situ generation 1123 salts 1587 addition of HCN 1212 imines, metalated 1265 and resonance 52 alkylation 1122 synthetic applications 1266 and ylids 52 imines, and aryl aldehydes 667 imines, N-benzylation 1120 hypostrophene 1414 and aza-Baylis-Hillman nitrile, [3+2]-cycloaddition and Cope rearrangement 1413 reaction, enantioselectivity 1029 hypsochromic shift 318 1166 of ketones 1488 and E/Z nomenclature 177 proton affinity 1097 IBX see iodoxybenzoic acid, and enamine salts 587 radical addition 1217 ortho and Hantzsch esters 1555 reaction conditions for ideal gas, and hydrogen bonding and hemiaminals 1111 formation 1114 110 and Mannich bases 1123 reagents for reduction 1554 ideal solutions, and ionic solvents and pinacol coupling 1595 imines, reduction, by silanes 1553 393 and pinacol coupling, reagents to amines 1553 +I Effect 21 1595 enantioselectivity 1555 –I effect 21, 362 and tautomerism 102 flow reactions 1554 imidazoles, and hypervalent and the Ugi reaction 1265 reagents 1554 iodine 1026 imines, aziridination 1207 transfer hydrogenation 1554 ligands 311, 920 azomethine, enantioselectivity 1554 reduction to aldehydes 1552 [3+2]-cycloaddition 1030 reagents 1554 with carboxylic acids by oxidation of amines 1491 strained 1023 1243–1244 by reduction of oximes, strained bicyclic 218 catalysts 1528 enzymes 1564 sulfonyl 1122 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2019

tosyl, base catalyzed, from Stork enamine reaction by Fischer indole synthesis rearrangement to amino 587 1419 ketones 1369 hydrogenation, metal catalyst cyclopropanation 1073 cyclopropyl, rearrangement 1554 formylation 665 1407 hydrolysis 672 from amides 1597 with ylids 1208 loss of water 1113 from hydrazones 1419 imines, with alkynes 1164 preformed 1123 SEAr reactions 624 with benzylic halides 1217 reaction with HONO 761 via Neber rearrangement 1369 with boranes, radicals 1165 reactivity 1124 with carbon dioxide, and metal with boronates, reduction to amines 1554 catalyst 668 enantioselectivity 1165 stability 1113 indolines, preparation 515 metal catalyzed 1165 with Oxone 1014 induced dipole 17, 20 with boronic acids 1165 imino esters 1106 induced ring current 54 metal catalyzed 1165 and Hoesch reaction 672 inductive destabilization of groups with carbenes 1167 and ketone formation 672 454 with diazo compounds, metal and the Chapman inductive effects 20 catalyzed 1167 rearrangement 1435 and alkyl groups 894 with diazoketones 1263 and the Pinner synthesis 1106 and bond polarization 21 with dienes 1054 from amides and phosphorus and carboxylic acids 21 with Grignard reagents 1162 pentachloride 1435 and hybridization 22 metal catalyzed 1163 from nitriles and alcohols 1106 alkene substituents 894 with ketenes 1261–1262, 1565 hydrolysis 1106 infinitely degenerate Cope enantioselectivity 1262 rearrangement to amides 1435 rearrangement 1412 intramolecular 1262 imino-ene reactions 953 infrared see IR ultrasound 1263 in-in isomers 182 Ing-Manske procedure 623 with metals 1262 in–out isomerism 111 inhibitors, and radicals 844 with nitro compounds, in–out isomers 181–182 initiation step, radicals 840 enantioselectivity 1166 inclusion compounds 114, 122, initiators, Grignard reagents 747 with organolithium reagents 125 radical 981 1162 and rotaxanes 130 radical, azobis compounds with organometallic reagents, rotaxanes 130 970 ionic liquids 1163 thiourea 123 inorganic esters, with alkoxides sonication 1164 indacene, and antiaromaticity 494 with silanes, enantioselectivity 86 insertion reactions, alkenes 1168 1165–1166 indanol derivatives 728 and carbocations 725 with silyl enol ethers 1182 indanones 663 and carbonyl nitrenes 716 with silyl ketene acetals 1182 indene, pKa 64 and dihalocarbenes 272 with sulfonic acids 1264 Index Chemicus 1625 and halocarbenes 726 with tellurium ylids 1207 Index of Reviews in Organic and nitrenes 277 with trifluoroborates 1166 Chemistry 1622 by carbenes 725 iminium ions, and Eschenmoser’s Index of Scientific Reviews 1622, by nitrenes 714 salts 1124 1639 enantioselective 715 and the Bruylants reaction 568 indicators, and acidity scales 353 mechanism 715 dienophiles 1053 and solvent acidity 352 metal catalyzed 715 hydrolysis, and Stork enamine and spectrophotometric carbenes 272, 1068, 1073 reaction 1098 measurements 352 and dirhodium catalysts 726 mechanism 1098 for pK, 2,4-dinitroanilinium ion intramolecular 729 protonolysis 235 352 diazocarbonyls 728 with Grignard reagents 568 for pK, o-nitroanilinium ion diazoesters 1168 iminium salts, addition of cyanide 352 enantioselective 495 1212 indirect hydration, with intramolecular 725 and Fischer indole synthesis ammonium salts and methylene 725 1420 TMSCl 913 N—H 729 and Hoesch reaction 672 indium, and alkyl aryl coupling nitrogen 713 and reductive amination 1119 562 O—H 729 chiral 1015 and selenide formation 510 of alcohols 729 conversion to amines 1165 compounds, and acetal cleavage of amines 729 conversion to diamines 1595 488 oxygen 1365 formation of nitriles 672 reagents, with alkynes 949 pyrrolidine derivatives 729 fragmentation of amines 1321 indole nitriles, formation 673 I strain see strain from dialkylamino halides indole-2-sulfones 642 π interactions with cations 113 1321 indoles 673 with CH 113 from oxazines 591 and nitroalkenes 977 aromatic compounds 113 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2020 SUBJECT INDEX

π–π interactions 113 intramolecular, acyl addition 981 intrinsic free energy 292 and catenanes 129 addition, alcohols to alkenes inverse electron demand, interconversion, 917 Diels-Alder reaction 1045 diene-cyclobutene 1392 aldehyde–carboxylic acid heteroatom-Diels-Alder interfacial mechanism 476 anions 1184 reactions 1054 inter-halogen compounds, with aldehydes, with inverse isotope effects 305 alkenes 992 organometallics 1143 inversion barrier, buckybowls 92 interlocked catenanes 129 aldol condensation 1178 E/Z for vinyl radicals 255 intermediates, allenes 700 alkenes with ketones 950 inversion of configuration, and and CIDNP 294 amidation of alkenes 930 azide ion 419 and free energy 286–288 arylation 880 and chlorination of alcohols and IR, NMR, and Raman Baylis-Hillman reaction 1151 441 294 Cannizzaro reaction 1601 and organocuprates 558 and mechanism 294 carbomagnesiation 947 and SN2 reactions 405 and ReactIR 294 coupling, palladium catalyzed and solvolysis 419 arenium ions 608 566 and substitution 689 bromonium ion 893 cyclization 939 at sulfur 140 carbenoid 1074 [2+2]-cycloaddition 1059 bowl-to-bowl 92 carbocations 225, 1214 [3+2]-cycloaddition 1033 fluxional 138 cyclopropane 1339 metal catalyzed 1034 of phosphorus 183 cyclopropenium 496 Diels-Alder reactions 1042 pyramidal 138 detection of 294 tether length 1043 and bridgehead atoms 139 diion 1065–1066 ene reaction 953 and carbanions 243 diradical, [2+2]-cycloaddition Gomberg reaction 831, 1131 and enantiomers 139 reactions 1066 Heck reactions 812 N, P, As, Sb 140 free-energy profile 287 hydration 915 energy barrier 138 halonium ions 893 hydroamination 926 iodide ion, lithium cleavage of in reduction, diimides 1552 metal catalyzed 926 carboxylic esters 542 in the Schiemann reaction hydrogen bonding 108 radioactive, and SN2 407 829 insertion 725 vinyl, conversion to isolation of 294 insertion of carbenes 729 vinylsilanes 547 organocuprate 556 ketenes with imines 1262 with boranes and base 1388 oxocarbenium ions 1214 ketones, with organometallics iodides, aryl, conversion to amides intermediates, radicals 254, 294, 1143 669 477 McMurry coupling 1597 with aromatic compounds, and CIDNP 253 Michael reactions 957–958 photochemistry 879 Grignard reagents, and oxygen intramolecular, nucleophilic with carbon monoxide 664 734 substitution 837 with carbon dioxide 664 intermediates, reaction 286 organocatalytic, Diels-Alder iodides, Finkelstein reaction 534 Reformatsky reaction 1153 reactions 1042 from PPh3 and I2, in ionic sulfenes 1313, 1418 oxy-Michael reaction 977 liquids 537 tetrahedral 377, 450 Paterno-Buchi¨ reaction, vinyl, from vinyl bromides 534 trapping 295 photosensitization 1061 iodination 858 ylids 1307 Pauson-Khand reaction 986 aromatic 645 intermolecular hydrogen bonding pinacol coupling 1595 aromatic compounds, 108 proton-transfer 350 solvent-free 646 internal conversion 321 rearrangement, mechanism 682 arylboronic acids 646 internal, Friedel-Crafts acylation photochemical 328 benzamides 646 660 Schmidt reaction 1373 continuous flow 337 internal nucleophilic substitution Scholl reaction 657 of aldehydes and ketones 705 see substitution, SNi Sonogashira coupling 818 reagents 705 internal return, and ion pairs 415 Stille coupling 717 iodine azide, addition to alkenes and SN1 reactions 415 Suzuki-Miyaura coupling 799 1002 and stereochemistry 416 Thorpe reaction 1209 iodine catalysts 649, 978 internal strain see I strain, strain trimerization of alkynes 1077 iodine cation 993 International Union of Pure and Ullmann reaction 797 iodine, cocatalysts, with Applied Chemistry see Williamson ethers synthesis hypervalent iodine 1454 IUPAC 492 iodine, Hunsdiecker reaction 886 interrupted Nazarov 958 Wittig reactions 1201 iodine, hypervalent 508 See also intersystem crossing 322 intrinsic acidity 372 hypervalent iodine and angular momentum 323 intrinsic barriers 292 with an iodine catalyst 1454 intimate ion pairs 415, 442 to SN2 reactions, and strain alternative reagents of oxidation and SNi reaction 440 energy 424 of alcohols 1454 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2021

and Dess-Martin periodinane and stereochemistry 416 and nitration of aromatic 1453 and the SN1 mechanism 414 compounds 631 and iodoxybenzoic acid 1453 contact 415 and palladium catalyzed and lactone formation 501 destruction, and SN2 reactions coupling 565 and oxidation of alcohols 1453 417 and phosphorus ligands 311 oxidation of alcohols, and diazonium salts 772 and pyrrole alkylation 515 microwaves 1454 formation, and SN2 reactions and reactions of epoxides 541 solvent free 1454 417 and SN2 reactions 470 with alkynes 597 intimate 415, 442 and Stille coupling 718 iodine, promoter for the Prins intimate, and SNi reactions 440 and Sulfonation, of aromatic reaction 1214 mechanism 418, 836 compounds 641 with cyclooctadiene 214 and E1 reactions 1281 and sulfur ylids 1206 with formic acid and amines solvent separated 417 and TEMPO oxidation of 1239 tight 415 alcohols 1452 iodo-saccharin, aromatic and Friedel-Crafts alkylation and the Baylis-Hillman reaction iodination, ionic liquids 652 1150 646 ion radicals, and cyanation 724 and the Beckmann iodocarbonyls, radical cyclization ion–dipole complexes, SN2 409 rearrangement 1375 974 ion–dipole interactions 121 and the Dakin reaction 1474 iodocyclopentane, reaction with ion–molecule pairs, and SN1 415 and the Glaser reaction 876 silver perchlorate 76 ion–radical pairs, and SNAr and the Henry reaction 1185 iodoesters, conversion to lactones reactions 770 and the Ritter reaction 1258 971 ionic bonds, and electronegativity and the Williamson reaction iodoform, and chromous chloride 19 491 1070 and hard acids and bases 361 and thiirane formation 509 iodohydrins 996 ionic configuration, and bond ionic liquids, aryl halides with iodoimidazolium catalyst 569 energy 31 amines 786 iodolactonization 998 and bond energy 32 arylation of amines 786 and radical cyclization 973 ionic Diels-Alder reaction, aza-Diels-Alder reactions 1053 iodonium ions see halonium catalysts 1037 aziridination of alkenes 1024 addition of iodo azide to ionic hydrogen bonds 107 Baylis-Hillman reaction 1151 alkenes 1002 ionic liquids 393, 636 Beckmann rearrangement 1376 iodonium salts, amination, acidic Lewis acidic 395 Bmim 394 aromatic compounds 635 addition of haloamines to Buchwald-Hartwig cross and aryl carboxylic acids 667 alkenes 1001 coupling reaction 787 diaryl, coupling with arenes alcohols, oxidation with Cr(VI) carboxylate salt alkylation 500 803 1447 carboxylic acids, with alcohols formation of carboxylic acids aldol condensation 1177 1229 667 alkene dihydroxylation 1006 catalyst, hydroamidation, of with thiols 783 alkene metathesis 1429 alkynes 931 iodosaccharin 997 allyltin compounds 1138 catalytic hydrogenation 1514 iodoxybenzoic acid, and oxidation amides, from esters 1246 chiral 394, 965 of alcohols 1453 ionic liquids, and acidity 352 Claisen rearrangement 1416 ortho 1453 and aromatic halogenation 644 cleavage of ethers 540 ion exchange resins, and sodium and aromatic nitration 632 conversion of alcohols to alkyl tetroxide 1006 and Baeyer-Villiger halides 538 ion pairing, and anti-elimination rearrangement 1378 coupling 567 1280 and carbenes 1071 CuCN and aryl halides 794 and rearrangements 1343 and conjugate addition 956 cyclization of alkenes to and syn-elimination 1279 and Dess-Martin periodinane alkanes 939 ion pairs, allylic carbocations 442 1454 [3+2]-cycloaddition 1032 and Criegee mechanism 1467 and dihydroxylation 1008 cyclopropylcarbinyl and E1 reactions 1281 and elimination 1312 rearrangement 1357 and E1cB mechanism 1286 and ether formation 491 deep eutectic solvents 395 and internal return 415 and Fischer indole synthesis DiBuIm 394 and isotope labeling 416 1419 Diels-Alder reaction 1037 and MO calculations 417 and halogenation of alcohols dihydroxylation 394 and ozonolysis 1467 538 of alkenes 1006 and phase transfer catalysis 476 and hypervalent ionic reagents droplet microreactors 337 and SN1 reactions 414–415 1454 ene reaction 952 and SN1′ reactions 441 and Lewis bases 395 epoxidation 1011 and SNi’ reactions 444 and Michael reaction 956 ethylpyridinium and solvent effects 225 and microwave reactions 395 tetrafluoroborate 394 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2022 SUBJECT INDEX

ionic liquids, aryl halides with and SN1 reactions 410 Ireland-Claisen rearrangement, amines (Continued) and superacids 414 Claisen rearrangement formation of cyclic amines 515 chlorotriphenylmethane 228 1417 Glaser reaction 877 of carboxylic acids, table 373 enantioselective 1417 Grignard reagents 1129 of diazonium compounds to iridium, magnetite impregnated, halogenation of alcohols 537 carbocations 235 catalyst 569 HBuIm 394 of leaving group, in SN1 iron, and metallocenes 66 ionic liquids, hydrogenation of reactions 411 catalysts, and cross coupling aldehydes or ketones 1543 of protonated alcohols to 561 aromatic compounds 1523 carbocations 235 complexes 116 hydrolysis of nitriles 1100 ionization, rate, and azide ions of cyclobutadiene 74 hydroxylamine 1115 419 compounds, and acetal cleavage imidazolium salts 393 of sulfonate esters 471 488 Imines, with organometallic ionizing power of solvents 472 iron pentacarbonyl, with Grignard reagents 1163 ions, and rearrangement, leakage reagents 743, 821 in catalytic hydrogenation 1515 1343 with organolithium reagents iodides, from PPh3 and I2 537 as guests in crown ethers 120 821 iodo-saccharin, aromatic binding by crown ethers 119 irregular serial publications, table iodination 646 bridged see bridged ions 1624 Knoevenagel reaction 1187 bridged, and halogenation of isobenzylfuranone 497 Lewis bases 395 alkenes 992 isoborneol 1351 methylimidazolium ions 393 cryptate 476 isobutane, and dipole moment 20 Michael reactions 955 halonium 992–993 and superacids 226 nitriles, by oxidation of amines nitrenium 278, 837 bond energy 30 1460 singlet and triplet 278 isocyanate ion, with alkyl halides oxidation, of alcohols 394, pentacoordinated 224 479 1457 radical see radical ions isocyanates, addition of alcohols of thioethers 1506 ipso attack, aryl radicals 854 1105 pyridinium ions and pyridinium Boyland-Sims oxidation 674 addition of amines 1125 salts 393 electrophilic aromatic by carbonylation of azides 764 reductive alkylation of alcohols substitution 625 by Hofmann rearrangement 1105 ipso carbon 614 1370 Suzuki-Miyaura coupling 800 and the SNAr mechanism 768 by Lossen rearrangement 1372 tetramethylguanidinium cation rearrangement 633 by rearrangement of acyl based 393 substituent migration 633 nitrenes 1336 Wohl-Ziegler bromination 862 ipso substitution, formation of aryl by the Curtius rearrangement ionic mechanism, alkenes, with boronates 793 1371 trialkylsilanes and acids and aromatic substitution 620 by the Schmidt reaction 1373 1520 IR (infrared) 1621 by thermolysis of acyl azide ionic melts, Fries rearrangement and acidity 352 1371 676 and carbenes 268 carbonylation of amines 764 ionic polymer supported OsO4 and carbocations 225, 233 catalytic hydrogenation 1556 1009 and conformations 188 conversion to amides 669 ionic solvents see ionic liquids, and Friedel-Crafts acylation conversion to β-thiolactams solvents 661 1264 and ideal solutions 393 and Friedel-Crafts alkylation dioxirane oxidation to nitro and substitution 483 651 compounds 1503 and the liquids 394 and hydrogen bonding 109, isocyanates, from acyl azides ionic strength, and acidity or 112 1336, 1371 basicity 373 and intermediates 294 from acyl halides 533 and rate of reaction 412 and mechanism 296 from acyl nitrenes 1336 and SN1 reactions 412 and strained aromatic from alkyl halides 533 ionic transition states, and polar compounds 218 from alkyl halides and solvents 469 and tert-butyl cation 224 isocyanate 479 ionization potential 13 and triphenylmethyl radical from amides and hypohalites and electronegativity 17 255 1369 and hardness 360 carbene with alkenes 1068 from amines and phosgene and PES 214 cyclobutadienes 73 1239 in keto-amines 214 cyclooctynes 216 from azides and carbon ionization ratio 354 methanonium ion 697 monoxide 764 ionization, and carbocation methyl radical 259 from carboxylate anions 1260 formation 235 of methane 12 from carboxylic acids and and carboxylic acids 372 step-scan time-resolved 251 hydrazoic acids 1373 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2023

from nitrile oxides 1437 and silicon 12 oximes 1115, 1338 from O-acyl hydroxamic acids and stability 216 selectivity in the Wittig reaction 1372 and steric hindrance 178 1199 hydrolysis 1105, 1370–1373 fused ring systems 180 isomers, fluxional 179 oxidation with dioxiranes 1503 heat of combustion 178 in-in 182 reaction with carbamates 1105 conformational, and conformer and proton transfer 351 reduction 1105 188 in–out 182 to amines 1565 cyclobutadienes 73–74 levo 134 with alcohols, mechanism 1105 dextro 134 out–in 181 with alkenes 1263 isomerization, and biphenyls 685 and bis(phosphoranes) 183 with enamines 1263 and reverse Friedel-Crafts and cryptates 182 with Grignard reagents 1168 alkylation 681 and proton transfer 351 with lithium aluminum hydride cis-trans, and isotope effects quaternary ammonium salts hydroselenide 1105 307 181 with phosphine oxides, isotopic mechanism 294 racemization 182 labeling 1260 photochemical 328 out–out 182 mechanism 1260 double bond 699 positional, isomerization of with water 1372–1373 Baylis-Hillman reaction alkenes 908 isocyanides 481, 1264 See also 1152 r symbol 180 isonitriles E/Z, azo compounds 638 syn/anti, from reaction at and hydrogen boding 111 enolate anions 1174 carbonyls 1088 and hydrogen bonding 111 Hofmann-Martius reaction t symbol 180 from amides 1327 680 transitional, rotaxanes 128 microwave irradiation 1328 N-nitroso to C-nitroso 634 valence bond 179 1,2-rearrangement 1384 of alkenes 1445 valence, and tosyl, and the Knoevenagel of alkyl boranes 1314 [2+2]-cycloaddition 1063 reaction 1188 of allylic alcohols, metal isonitriles see isocyanides Ugi reaction, isocyanide free catalysts 1367 isonitriles, and cyanide ion 600 1265 of azo compounds 638 conversion to isothiocyanates with Grignard reagents 1265 of azobenzenes 910 533 with organolithium reagents of biphenylene 1399 dehydration, of amides, 1265 of boranes 1368 reagents 1327 with water 1264 of carbenes 268 to isonitriles, reagents for isodesmic reactions 39 of conjugated acyl radicals 1328 isoindolines, preparation of 515 842 from alcohols 527 isoindolinones 789 of conjugated carbonyls 909 from amines 526 isoinversion 693 of cyclopropane, carbene from epoxides 527 isolable ozonide 1469 intermediate 272 from formamides 527 isolation, of intermediates, Neber of double bonds 698 from oxetanes 527 rearrangement 294 of terminal alkynes, allene reduction to amines 1557 isomerism see isomers intermediates 700 with alkynes 1169, 1264 isomerism, in–out 111 out of conjugation 909 with Grignard reagents 1169 and carbocations 111 photochemical, alkenes 700 with organolithium reagents isomerization, alkenes 699 cyclooctene 328 1169 allylic-propenyl 908 propargylic compounds 909 isopentane, bond energy 30 asymmetric 909 radicals 898 isopropyllithium, and X-ray 247 in hydration of alkynes 915 terminal alkynes 700 Isoquinolines, by radical metal catalyzed 909 thermal, cyclization 975 isomers, amides 177 dibenzosemibullvalenes from alkynes 928 and 2n rule 180 329 N-oxides, chiral 1504 and configuration 188 distributions, electrophilic Pictet-Spengler reaction 655 and enantiomers 134 aromatic substitution 625 SEAr reactions 624 and heat of atomization 29 isomers, E/Z, and isoracemization 692 and rotaxanes 128 carbon-heterocycle double isothiocyanates, addition to and the 2n rule 177 bonds 176 alkenes 1000 annulenes 77 and radicals 255 amines to carbon disulfide 1127 cis-trans 144, 175–178, 180 and strained bicyclic imines catalytic hydrogenation 1556 and conformations 192 218 conversion to thioamides 669 and cyclooctene 177 azo compounds 329 amines and thiophosgene 1240 and diastereomers 175–178 Cahn-Ingold-Prelog system from chlorothionoformates and monocyclic compounds 176 1328 179 enol ethers 721 from dithiocarbamic acid salts and restricted rotation 219 isomerization of alkenes 908 1127 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2024 SUBJECT INDEX

isothiocyanates, addition to and the Shapiro reaction 1309 IUPAC mechanisms, and carbenes alkenes (Continued) and the tetrahedral mechanism 468 from isonitriles 533 1090 and diazonium salts 467 hydrolysis 1105 benzidine rearrangement 1423 aromatic substitution 614 reduction to amines 1565 carbon dioxide 1161 E2 reactions 1274 with alcohols 1105 deoxygenation, of sulfoxides SN1 reactions 892 isothiouronium salt, from thiourea 1591 IUPAC nomenclature, 506 rearrangements, sigmatropic addition–elimination isotope effects 489 1400 mechanism 446 and arenium ions 610 sulfonyl sulfur, nucleophilic bridged systems 210 and carbocations 227 substitution, mechanism enantiomers 159 and Chugaev reaction 1305 1266 for mechanisms 398 and cis-trans isomerization 307 isotopes, and acetal hydrolysis for transformations 398 and E2 reactions 1277 486 Schleyer adamantization 1353 and hyperconjugation 306 and alkynyl carbocations 448 SN1′ reactions 441 and mechanism 304 and chirality 146 SN2′ reactions 443 and NMR 305 and hydrolysis 1225 SNi reactions 440 and phenonium ions 433 and ion pairs 416 system, SN1 reactions 411 and rearrangements 1339 and SN2 reactions 407 Ivanov condensation 1176 and SE1 reactions 691 and solvolysis 416 and temperature 307 effects 1285 Jablonski diagram 321 and the Chugaev reaction 1305 secondary isotope effect in Jacobsen reaction 685 and the SN2 reaction 307 substitution reactions 456 and rearrangement 685 and transannular hydride shifts isotopic dilution, and enantiomeric Jacobsen-Katsuki epoxidation 1435 purity 175 1017 isotope effects, arenium ions 609 isotopic effect, and bridged Jahn-Teller effect 76–77 influence of base 610 radicals 848 Japp-Klingemann reaction 711 isotope effects, aromatization isotopic exchange, aldehydes and Johnson polyene cyclization 944 1443 ketones 703 Jones reagent 1447 Baeyer-Villiger rearrangement isotopic labeling 65 and oxidation of alcohols 1447 1380 aldehyde or ketone with OsO4 1471 calculations 305 rearrangements 1360 Journal of Synthetic Methods Cope elimination 1296 and cyanogen bromide 295 1625 deuterium 304 and mechanism 295 Journal of the Chemical Society, and dissociation energy 304 and NMR 296 and literature searches deuterium ion 610 and radical rearrangements 1632 E1-E2-E1cB spectrum 1287 1347 journals, chemical literature E1cB mechanism 1284 and the Stevens rearrangement 1610–1612 heavy-atom 305 1381 current, table 1610–1612 inverse 305 and the Wallach rearrangement discontinued 1610–1612 kinetic 405 1436 how to locate articles 1639 partitioning effect 609 Favorskii rearrangement 1362 irregular publications 1622 reaction with the nitrosonium Fischer indole synthesis 1420 languages 1609 ion 634 phosphine oxides with literature 1608 secondary 306 isocyanates 1260 review, table 1623 SN1 reactions 771 Pummerer rearrangement 1603 reviews 1622 SNAr reactions 770 rearrangement of supplementary information solvent 307 N-nitroanilines 805 1609 tritium 305 Steven’s rearrangement 1381 Julia-Colonna epoxidation 1016 isotope labeling see labeling Wolff rearrangement 1365 Julia-Kocienski reaction 1203 isotope labeling, alkynes 449 isotopic UV 154 Julia-Colonna´ epoxidation 1016, and aromaticity 65 isovalent hyperconjugation 94 1206 and chirality 147 isoxolazine N-oxide 1504 and E2 reactions 1277 IUPAC, and spectroscopy 13 Kamlet reaction see Henry and Fischer indoles synthesis mechanisms, substitution reaction 1420 reactions 465 Kamlet reaction 1185 and oxidation of Cathecols and nomenclature, of carbocations Katritzky pyrylium-pyridinium hydroquinones 1460 224 method 501, 1585 and ozonolysis 1469 SE2 reactions 688 and alkyl halides 543 and reverse Friedel-Crafts mechanism 694 and thiocyanates 512 alkylation 682 SEi′ mechanisms 694 reagents 578, 1585 and the benzyne mechanism terminology for acids and bases Keck allylation, allyltin 1138 772 339 organometallics 1138 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2025

Kekule´ structures 60 with phosphorus ylids 1201 ketones, acetal formation 1101 and polyacenes 61 with thiols 923 acid catalyzed rearrangement kekulene, and NMR 84 ketenimines, conversion to 1359 ketal formation, mechanism 1102 amidines 1122 mechanism 1360 ketals see acetals ketenyl radicals 842 acidity of α-hydrogen 1110 ketals, and enol ethers 1103 ketimines, [2+2]-cycloaddition acylation 1253 and transacetalization 1103 1058 α-acyloxylation 871 from alcohols and ketones 1101 ketimines, reduction, reagents ketones, addition of alcohols 1101 from internal alkynes 918 1555 of allylic boranes, with hydride reagents 1574 reduction, transfer enantioselectivity 1145 ketene acetals, conversion to hydrogenation 1554 of diazomethane 1365 oxetanes 1261 keto acids, decarboxylation 752, of thiols 1107 silyl 1180 754 of water 1095 silyl, conjugate addition 967 from metalated imines 1266 ketones, alkylation 579–580 ketene-imine nitranion 240 metal catalyzed decarboxylative with alcohols 584 ketene-iminium salts, allylation 887 chiral amines 584 electrocyclization 1392 oxidative cleavage of cyclic Stork enamine synthesis 587 ketenes, and enamine acylation alkenes 1470 ketones, amination and 587 keto esters, and acetoacetic acid microwaves 714 and formation of carbenes 270 synthesis 577 amino, and the Mannich Arndt-Eistert synthesis 1364 base catalyzed condensation of reaction 1123 conversion to cyclobutanones esters 1253 amphiprotic properties 701 1057 cleavage with base 757 ketones, and amide bases 1253 cyclic, from diazoacetate 1358 cyclic, Dieckmann Baeyer-Villiger rearrangement [2+2]-cycloaddition condensation 1253 1378 1057–1058 decarboxylation 753 bisulfite addition products 1111 dimerization 1065, 1261 from aldehydes 723 carbanions 250 from acyl carbenes 273 with hydrazines 1117 Collman’s reagent 602 from acyl halides 1313, 1320 keto form of carbonyls, stability and hemiaminals 1111 from carbenes 274 701 and hydrogenolysis 1577 from carboxylic acids, reagents keto form thermodynamic and Japp-Klingemann reaction 1304 stability 98 711 from diazoalkanes 271, 1262 keto aldehydes, and aliphatic and McMurry reaction 1597 from diazomethane 270 Vilsmeier reaction 720 and Peterson alkenylation 1191 from the Wolff rearrangement keto-enol tautomerism 701 and Piers hydrosilation 1541 1364 See also tautomerism and reagents for hydrolysis of hydrolysis 1364 acid catalyzed 702 C=N compounds 1097 to carboxylic acids 1364 and microscopic reversibility and tautomerism 97 in situ formation 1313 702 and the Barbier reaction 1136 metal catalyzed dehalogenation and torsional strain 702 and the Haller-Bauer reaction of acyl halides 1320 base catalyzed 702 759 photolysis of 328 Claisen rearrangement 1416 and the Knoevenagel reaction preparation in flow reactors 338 enolate anion equilibrium 1187 reaction with water 1364 703 and the Mannich reaction 1123 via Wolff rearrangement 274 proton transfer 701 and the Reformatsky reaction with alcohols 919, 1364 solvent effects 701 1152 with aldehydes or ketones 1260 keto-esters, by the Reformatsky and the Willgerodt reaction with amides 1249 reaction 1153 1604 with amines 1122 from ketones and diazoesters and Tollens’ reagent 1193 with ammonia or amines 1364 1366 ketones, aryl 670 with anhydrides 1253 keto-nitriles, by the Thorpe and imino esters 672 with carbenes 1070 reaction 1209 from Grignard reagents 670 with chloroimines, keto-sulfones, alkylation 577 from nitriles 672 enantioselectivity 1262 keto-sulfoxides, alkylation 577 Hoesch reaction 672 with cyclopentadiene, ketocarbenes 1364 ketones, arylation 819 [2+2]-cycloaddition α-ketols, rearrangement 1360 and palladium-catalysts 819 reactions 1064 ketone esters, McMurry reaction ketones, asymmetric amination orbital overlap 1065 to give cyclic ketones 714 with hydrazones 1262 1597 azine formation 1116 with imines 1261–1262, 1565 ketone-ene reaction, transannular base cleavage, and strain 758 enantioselectivity 1262 954 steric effects 758 intramolecular 1262 1,4-ketones, from 1,3-ketones base induced deprotonation ultrasound 1263 1366 7037 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2026 SUBJECT INDEX

ketones, asymmetric amination and Nazarov cyclization 958 enol content 98 (Continued) conjugate addition of enzymatic reductions 1541 bicyclic, and thermal extrusion carbamates 977 ketones, epoxy see epoxy ketones of carbon monoxide 1324 from allenes 444 epoxy 1017 by carbonylation of alkynes from ketones 1446 conversion to hydroxyl acids 985 halogenation 708 1362 by carbonylation of allenes via Robinson annulation fluorination 705 985 reaction 1179 ketones, formation, of enamines borane reduction reagents 1539 with aldehydes, and radicals 1111 bromo, alkylation with boranes 1217 of enolate anions 1172 592 with boranes 967 of enols 1174 ketones, by acetoacetic acid ketones, conversion to acetals of esters 1103 synthesis 577 1102 of halo-ketones 704 by acid catalyzed rearrangement to aldehydes 1195 of hydrates 1095 of epoxides 1355 to amides 1604–1605 of nitroso compounds 710 by addition of aldehydes to to amino alcohols 1596 of oximes 710 alkenes 981 to enol thioether 1109 of oxocarbenium ions 1360 by carbonylation of aryl halides to gem-difluoro compounds of thioketones, with hydrogen 821 1128 sulfide 1107 by DMSO-type oxidation of to sulfides 1110 ketones, formylation 720 alcohols 1451 ketones, coupling to form akenes Friedel-Crafts alkylation 653 by Fries rearrangement 675 1597 ketones, from acid chlorides 604 by hydrolysis of C=N ketones, cyclic, and I strain 380 from acyl halides and compounds 1096 and reactivity 380 organometallics 670 by hydrolysis of imines 1491 and the Schmidt reaction 1374 from aldehydes 589, 722, 981, by Oppenauer oxidation 1450 aromatization to phenols 1443 1366 by oxidation of alcohols 1447 Baeyer-Villiger rearrangement from alkenes 1500 of alkenes, reagents for 1499 1378 oxidizing reagents 1499 of amines 1491 by expansion of bicyclic from alkoxide cleavage 755 of cyclic alkanes 1477 ketones 1366 from alkyl halides 604, 969 by oxidative cleavage, of dihalides and Collman’s reagent from alkynes 915–916 alkenes 1470 602 from allylic alcohols 1367 of diols 1463 from acid catalyzed from amines 1492 by ozonolysis of alkenes 1466 rearrangement of amino from aromatic compounds 658 by pyrolysis of allylic ethers alcohols 1357 from aryl acyl halides 670 1329 from dicarboxylic acids 1257 from aryl halides 822 by rearrangements of from organometals with from arylboronic acids 822 hydroperoxide 1380 conjugated esters 1143 from boronic acids with nitriles, mechanism 1380 hydroacylation 979 metal catalysts 1169 migratory aptitude 1381 McMurry reaction with keto from carboxylic acids 1154, by the Meyers’ reaction 591 esters 1597 1257 by the Nef reaction 1098 oxidative cleavage, to and organolithium reagents by the Wacker process 1499 dicarboxylic acids 1465 1153 ketones, catalytic hydrogenation reagents for 1465 and radicals 1257 1536 ring expansion 1366 from carboxylic esters and chemoselective reducing agents with hydrazoic acid 1374 organometallics 1157 1533 ketones, cyclopropyl, with Lewis from cleavage of diketones 757 chiral, and chiral amide base acids 598 from conjugated ketones 895 704 from conjugated ketones 1206 from cyanoboranes 1387 α-chloro, precursors to thiiranes ketones, decarboxylative from dialkylcadmium reagents 493 alkylation 585 670 cleavage with amide bases 759 dehydrogenation 1446 from dicarboxylic acids 1475 with base, solvent effects deoxygenation 1577 from dicobalt octacarbonyl 742 758 diaryl, from organometallics from dihalides 484 haloform reaction 757 723 from diols 1354 condensation with esters 1183, diazo 712, 726 from dithianes 589 1255 dibromo and dichloro 707 enol borinates 967 ketones, conjugated 719 See also difluorohomologation 1366 epoxides 1355 conjugated ketones dihalogenation 706 metal catalysts 1355 α-acyloxylation 871 divinyl 604, 742 from esters 675 alkylation 585 from vinyl organometallics ketones, from Grignard reagents and Meyer-Schuster 603 and formic acid 743 rearrangement 444 enamino, coupling 805 halo amides 1370 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2027

from halo amines 1321 less reactive than aldehydes with sodium in ethanol, from homoallylic alcohols 1089 mechanism 1537 1328 macrocyclic, conformation with tin hydrides 1540 from hydrazones 164 203 ketones, reductive amination 1118 from hydroperoxides 1381 mechanism of hydration 1096 reductive coupling to diols, from hydroxy–amines 1357 Meerwein-Ponndorf-Verley reagents 1593 from iminium salts 672 reduction 1538 regioselectivity of halogenation from ketones 1359 metal mediated addition of 705 from metalated imines 1266 haloesters 1152 relative reactivity, steric effects from nitriles 1168, 1475 halogenation 705 1089 from nitro compounds 1492 methyl, and the haloform steric hindrance and reduction from organolithium reagents reaction 758 1533 743 by homologation of sterically hindered, and with nitriles 1169 aldehydes with Wolff-Kishner reduction from organometallics 603, diazomethane 1366 1577 742 cleavage with halogen 757 structural variations and the from oximes 830 ketones, nitro, with amines 759 Wittig reactions 1196 from silyl enol ethers 570, 721 nitrosation, mechanism 710 sulfenylation 716 from silyl-epoxides 1192 α-oxidation to diketones 1487 symmetrical 742 from Stork enamine reaction with SeO2, mechanism 1487 thermal extrusion of carbon 586 reagents for 1487 monoxide 1324 from thioamides and Paterno-Buchi¨ reaction 1060 thioalkyl, from enolate anions organometallics 1159 phenylseleno 716 716 from thioesters 1158 photochemical unsymmetrical 742 from vinyl halides 483 [2+2]-cycloaddition, with halogenation, regioselectivity from vinylic compounds 485 alkenes 1060 706 ketones, halo, Favorskii photochemical cleavage 262 by hydroboration 1387 rearrangement 1361 photochemistry 317, 324 formation of silyl enol ethers from diazo ketones 543 photoreduction 330 721 radical ring expansion 1359 pKa 1171 regioselectivity 582 ring contraction 1361 Prins reaction 1214 ketones, with active hydrogen ketones, halogenation, and prochiral, reduction of 1542 compounds 1169 microwaves 704 protecting groups 1108 with alcohols 584 Dess-Martin periodinane 708 with alcohols, compatible with aldehydes, aldol enantioselectivity 705, 707 functional groups 1102 condensation 1173 flow reactions 707 with amines 1111 with alkenes 950 reagents for 704 with dienes 1053 intramolecular 950 ketones, Henry reaction 1185 with (trimethylsilyl)acetamide with alkyne anions 1143 heteroaryl, by carbonylation 721 enantioselectivity 1144 822 ketones, reduction, and Cram’s metal catalyzed 1143 homoallylic 327 rule 1546 with allylsilanes 1148 from keto acids 887 biocatalyst 1542 metal catalyzed 1148 ketones, homologation 1365 diastereoselectivity 1545 with allyltrichlorosilane 1149 hydration of 1095 enantioselectivity 1542 with amide bases 716, 1172 hydride reduction, mechanism hydrogen transfer 1541 with amines 1111, 1118 1535 Luche reduction 1533 and hydrogen 1118 hydrogenation, in ionic liquids metal hydrides 1533 metal catalyzed 1112 1543 to alcohols 1532 with azadienes 1055 hydroxy 1189 See also hydroxy to methylene, reagents for with carbanion named reactions, ketones 1577–1579 table 1170 from epoxy alcohols 1356 versus aldehydes 1533 with chiral hydrazines 164 hydroxyalkylation 653 with alanes 1540 with diazo compounds 1217 α-hydroxylation, with alkoxyaluminum hydride with diazo esters 1366 enantioselectivity 1484 1536 with diazoalkanes 1206 enzymes 1486 with aluminum isopropoxide with enolate anions 248 from silyl enol ethers 1484 1538 with esters 1183, 1255 metal catalysts 1483 with ammonium formates 1541 with Grignard reagents 1129 reagents for 1483, 1485 with Baker’s yeast 1541 with halo esters 1190 with enzymes 1483 with boranes 1539 with halogens 704 with oxygen 1483 with enzymes 1543 with HCN 1210 indirect carboxylation 1192 with hydrides 1532 with hydrazines 1115–1116 iodination 705 with metals 1537 with hydrazoic acid 1373 isotopic exchange 703 with sodium in ethanol 1537 with hydrogen sulfide 1107 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2028 SUBJECT INDEX

ketones, with active hydrogen and the Wittig rearrangement chromium (VI) oxidation of compounds (Continued) 1384 alcohols 1449 with hydroxylamine 1115 dimerization, and Grignard E1 reactions 1281 with isocyanides and carboxylic reaction 1134 fast reactions 301 acids 1265 radical ions 265 first order 412 with ketenes 1260 Kiliani-Fischer method, and and SE1 mechanism 691 with LDA 721 sugars 1211 rate law 301 with lithio-silanes 1191 Kimel-Cope rearrangement, reactions 297 with methoxyvinyllithium 1189 Claisen rearrangement Friedel-Crafts alkylation 652 with Mo peroxide, 1417 gas phase reactions 301 α-hydroxylation of enolate Kindler modification, Willgerodt Heck reaction 813 anions 1483 reaction 1604 inverse isotope effects 305 with MoOPH, α-hydroxylation kinetic acidity see acidity lead tetraacetate cleavage of of enolate anions 1483 kinetic control conditions 721 diols 1464 ketones, with nitro compounds aldol condensation 1174 methods for determining 300 1185 and sulfur ylids 1205 nitration of aromatic with nitrous acids 710 enolate condensation 582 compounds 632 with Nozaki-Hiyama reaction enolate reactions 582 overall rate 299 1141 kinetic effects 1285 periodic readings 300 with organoaluminium kinetic isotope effects 405, 678 pseudo first order 300, 405 compounds 1139 kinetic reactions, free energy, radical chain reactions 843 with organochromium energy profile 290 radical cyclization 972 compounds 1141 kinetic resolution 147, 169 rearrangement of enantioselectivity 1141 See also resolution cyclopropylcarbinyl with organocuprates 1143 amines 171 radicals 850 with organolithium reagents and enantiomeric purity 175 second order reaction 298 1129 aza-Cope rearrangement 1409 HBr with alkenes 910 with organometallics 166, Chemoenzymatic dynamic 172 reactions 297 1136 dynamic 581 SN1 reactions 412 elimination 1136 ketones 704 and leaving groups 411 enantioselectivity 1137 kinetically controlled reactions, reaction 771 intramolecular 1143 energy profile 290 reaction, and concentration metals used 1136–1142 kinetics, and aliquots 301 771 selectivity 1138 and bond rotation 303 SN2 reactions 405 with organotitanium and calorimetric methods 301 spectral readings 300 compounds 1140 and enthalpy 284 substitution at sulfur 1267 with organozinc compounds and entropy 304 very fast reactions 301 1140 and ESR 301 Kinusaga reaction 1263 enantioselectivity 1140 and frequency factor 303 Kishi’s NMR method, and with other organometallic and half-life 301 absolute configuration 155 compounds 1143 and homogenous reactions Knoevenagel condensation see with Petasis reagents 1202 297 Knoevenagel reactions with phenylhydrazine 1419 and ion pairs in the SN1 Knoevenagel reactions 1187 with phosphorus ylids 1194 reaction 414 acid catalyst 1187 with propargyl substrates 1145 and Marcus theory 298 and acyl anion equivalents with secondary amines 1113 and mechanisms 296, 303 1189 with sodium bisulfite 1111 and molecularity 298 and ammonium salts 1187 with sulfones 1188 and NMR 302, 412 and carbamates 1189 with sulfur ylids 1204 and pressure 300 and Darzens condensation 1190 with Tebbe reagent 1202 and quenching 300–301 and high pressure 1187 with the Nysted reagent 1203 and rate constant 297 and the homoaldol reaction with thiols 1108 and rate law 297, 299 1189 with ylids 1193 and rate-determining step 298 and the Wittig reaction Wolff-Kishner reduction 1577 and reactions 284 1188–1189 ketoximines, conversion to nitriles and salt effect 412 and tosylhydrazones 1189 1326 and SE1 reactions 692 and tosylisocyanides 1188 with Lewis acids 1326 and secondary isotope effects and ultrasound 333 ketyls, and Gomberg-Bachmann 306–307 diastereoselective 1188 pinacol synthesis 1593 solvent isotope effects 307 Doebner modification 1188 and reduction of carbonyls with and spectroscopic methods 300 domino reactions 1187 sodium in ethanol 1537 and steady state 299 enantioselective 1188 and the acyloin condensation kinetics, benzidine rearrangement heterocyclic compounds 1187 1599 1422 hydroxysulfonamides 1188 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2029

in ionic liquids 1187 lactams, alkylidene 975 with alkyl halides 529 metal catalyzed 1187 from ynamides 931 with amines at high pressure microwaves 1187 lactams, aminomethyl 514 1247 nitriles 1188 and determining absolute with boranes 1160 on silica gel 1187 configuration 154 with Grignard reagents 570 on zeolites 1187 and proton transfer 351 with Petasis reagent 1202 solvent free 1187 and strain 213 lactic acid, and absolute special variations 1188 Arndt-Eistert synthesis 1364 configuration 148 structural variations 1187 arylation 529 lactim ethers, vinyl, Diels-Alder suitable functional groups 1187 bicyclic, from carbamates 931 reactions 1053–1054 ultrasound 1187 bromo 1001 lactones, and conformations 203 Knoevenagel-type carbanions, by amidation of alkenes 930 and Mukaiyama reagent 1230 palladium catalyzed by Beckmann rearrangement and neighboring group coupling 565 1375 mechanisms 424 knots, molecular 130, 132, 147 by carboxylation of alkenes and Yamaguchi protocol 1231 and DNA 131 988 by alkene metathesis 1430 and metals 131 by halolactamization 998 by Baeyer-Villiger Koch reaction 982 by radical cyclization 973 rearrangement of cyclic Koch-Haaf reaction 604, 982 by Schmidt reaction with cyclic ketones 1378 KOH, with amines 505 ketones 1374 by carbonylation 604 Kolbe electrosynthesis see Kolbe carbonylation of alkenes 988 of alkenes 988 reaction conjugate addition to by halolactonization 998 Kolbe reaction 885 conjugated esters 977 by metathesis reactions 1430 and electron transfer 1441 conversion to thiolactams 1109 by oxidation, of cyclic ethers, mechanism 885 Diels-Alder reactions 1053 reagents 1488 Kolbe-Schmitt reaction 668 β-lactams 529 of diols, reagents 1494 Kornblum reaction 1490 and microwaves 1263 by radical cyclization 973 Kornblum’s rule, and ambident by [2+2]-cycloaddition 1058, by reduction of anhydrides, nucleophiles 481 1263 reagents 1580 Krapcho decarboxylation 753 conversion to azetidines 1549 β-lactones 1072 Krebs cycle, and enantiotopic 184 from enamines to isocyanates carbonylation of propargyl Krohnke¨ reaction 1491 1263 alcohols 988 and microwaves 1491 from imines 1057 [2+2]-cycloaddition 1058 Kumada coupling 807 from ketenes with imines 1262 decarboxylation to alkenes asymmetric 807 from β-amino esters 1247 1323 spirocyclic 1263 from ketenes with aldehydes or L. kefir, oxidation of hydrocarbons lactams, from acyl anilines 1494 ketones 1261 1476 from alkene–amides 1027 enantioselectivity 1261 labeling, and acetal hydrolysis from alkenes or alkynes 1027 pyrolysis to alkenes 1323 486 from amines 1488 lactones, chiral, and Cinchonidine and acetals 486 and alkynes 927 alkaloids 916 and aryl carboxylic acids 668 reagents 1488 from achiral lactones 1379 and carbene insertion 726 from amino acids 1243 via Bayer Villiger and decarboxylation 684 from anilines 1494 rearrangement 1379 and enantiotopic atoms 184 from cyclic ketones 1374–1375 lactones, conversion to and ion pairs 416 from cyclic oximes 1375 thiolactones 1109 and phenonium ions 433 from halo amides 1434 cyclic, via the Story synthesis and solvolysis 416 from imines 1488 1332 cyclopentadienide ion 63 from ketenes 1364 β-decarboxylation 1331 deuterium 440 from lactones 1247 dyotropic rearrangements in alkynyl carbocations 448 lactams, N-aryl 789 1437 isotopic, and mechanism 295 N-arylation 529 enolate anions 583 peroxyesters 871 N-formylation 1250 enols 100 tritium 448 N-halogenation 765 extrusion of carbon dioxide von Richter rearrangement 834 N-vinylation 529 1325, 1331 water 834 lactams, oxidation of amines 1488 formation, and photoredox laccase, oxidation of alcohols to hydroxylactams 1486 conditions 1027 1456 lactams, reduction to cyclic and ring size 286 lactamization 1243 amines 1582 rate constants 287 enzymatic 1243 ring expansion 1247 lactones, from alkenes 1026 lactams, alkylation 528–529 ring expansion from cyclic from alkynes 920 and microwaves 478 amines 765 from allenic alcohols 988 internal 529 sulfenylation 716 from cyclic peroxides 1332 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2030 SUBJECT INDEX

lactones, from alkenes (Continued) LC (liquid chromatography) and and strain 465 from dialdehydes and the diastereomers 168 and substitution reactions 464 Cannizzaro reaction 1601 and resolution 168 and the element effect 446 from dicarboxylic esters and LCAO 6 and the tetrahedral mechanism the Tischenko reaction LDA (lithium diisopropylamide) 1093 1602 369 and thiiranes 465 from diols, enantioselectivity LDA 579–580 leaving groups, aromatic 1494 aggregates of 369 amination 785 from epoxides, metal catalyzed and [3+2]-cycloaddition 1035 at saturated carbon 464 1359 and aldol condensation 1173 axial versus equatorial, in E2 from halo-acids 286 and allylic carbanions 1035 reactions 1278 from hydroxy carboxylate salts and anionic Fries azide 741 500 rearrangement 677 carbon dioxide 683, 1323, from iodo-alcohols 604 and carboxylic esters 1183 1325, 1331–1332 from iodoesters 971 and conjugate base 1171 carbon monoxide 1324, 1331 from lactones, ring expansion and elimination 1312 definition 280 1437 and the Claisen condensation diazonium group 823 from xanthates 1026 1183 diazonium salts 466 lactones, hydration of and X-ray crystallography 369 in SRN1 reaction 779 alkene–carboxylic acids with amides 1184 dimethyl sulfide 1490 915 with ketones 721 ditosylamines 501 hydrogenation 1548 lead tetraacetate, and ditosylates 466 large ring 1027 acyloxylation 871 E1cB mechanism 1283 macrocyclic, from cyclic and bis(decarboxylation) 1475 epoxides 567 ketones 757 and oxidative cleavage of diols H2S 1126 photolysis 1331 1463 halides 773 reaction of alcohols, with and oxidative decarboxylation ionization and the SN1 reaction carboxylic acids 1230 1475 411 reduction 1580 cleavage of diols, cyclic kinetics and SN1 411 sulfenylation 716 transition state 1464 nitrogen 466, 834, 1310, 1330, thermal extrusion of carbon mechanism 1464 1462, 1578 dioxide 1324 conversion of alcohols to cyclic order, nucleophilic aromatic transesterification 1233 ethers 866 substitution 779 with amines 1247 radical mechanism 1475 organomercury compounds, and with hypervalent iodine 501 leakage, and carbocations 1343 SE2 reactions 696 with metal carbene complexes rearrangement of ions 1343 other, in aromatic substitution 1203 leaving groups 404, 692 680 with Petasis reagent 1202 ability, table 468 proton 608 with Tebbe reagent 1202 amino, in Mannich bases 466 pyrylium salts 466 lactonization, Baylis-Hillman and amines 466 sulfates 567 reaction 1152 and aziridines 465 sulfonate esters 465–466 from cyclic dienes 1026 and basicity 465 sulfonates 567 of alkenes 1026 and carbene formation 468 sulfonyl groups 1267 ultrasound 1026 and carbocations 1351 sulfur dioxide 1317, 1331 Ladenburg formula 1063 and elimination 1294 β-substituents 422 Lange’s Handbook of Chemistry and epoxides 465 Lederer-Manasse reaction, 1620 and neighboring groups 422 Hydroxyalkylation 653 Lanthanide shift reagents 153, and nucleophilic aromatic Lemieux-von Rudloff reagent, 174 substitution 770, 779 oxidative cleavage of large angle strain see strain and nucleophilic substitution alkenes 1470 large rings, lactones 1027 452 length, bond see bond distance strain 215 and radical cyclization 974 length, cell, and specific rotation lariat ethers 120 and rate 1093 135 laser flash photolysis 225 and reactions 1288 Leuckart reaction 1121 Lavoisier’s definition, oxidation and rearrangement of nitrenes and the Wallach reaction 1121 1439 1336 leveling, carbon-14 295 Lawesson’s reagent 1109 and SE2 reactions 696 levo isomer 134 amides, from carboxylic acids and SEAr reactions 6284 Lewis acid catalysts 648, 1181 1243 and SN1 reactions 410, 1093 and steric effects 366 with alcohols 506 and SN2 reactions 1093 and the Prins reaction 1214 with ketones 1109 and SN2′ reactions 444 [3+1+1]-cycloaddition 1084 with carboxylic acids 1237 and solvent ionizing power hydrosilation of alkynes 942 with phosphonate esters 1305 472 Prins reaction 1215 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2031

steric effects 367 coupling alkenes with acyl LiBr, with enolate anions 248 sulfonyl halides with halo esters halides 720 library synthesis, and flow 559 definition 357 chemistry 337 Lewis acid–base complex 357 ethers with anhydrides 502 LICA 579–580 rate 358 for addition of alcohols to LIDAKOR reagent, and epoxides Lewis acidity, decreases going carbonyls 1101 1302 down the periodic table for addition of allylic silanes to lifetimes, carbanions 240 366 aldehydes 1148 diradicals 261 and Brønsted acidity 366 for rearrangement of epoxides of hydrogen bonds 106 Lewis acids 357–359 to ketones 1355 of radicals 850, 1348 acidity and solvents 372 for the Beckmann oxocarbenium ions 235 addition, of acyl halides to rearrangement 1375 radicals 252 alkenes 1005 Friedel-Crafts acylation 659, ligand transfer, cuprates, conjugate of thiols to alkenes 922 661–662 addition 961 allylsilanes with aldehydes, heteroatom Diels-Alder ligands, amines 44 enantioselectivity 1209 reaction 1052 and η-complexes 44 and acetal cleavage 488 lithium perchlorate 358 bisoxazoline 715 and acetals 488 reaction types 358 carbalong 89 and addition of alkyl halides to reversal of Friedel-Crafts carbon monoxide 116 alkenes 1003 alkylation 681 catalytic hydrogenation 1514 and alcohol dehydration 495 strength of 359 chelating 89 and arenium ions 612 used for the Ritter reaction chiral see chiral ligands and aromatic halogenation 644 1258 chiral 565 and Beckmann rearrangement Lewis acids, with alkanes 1353 and alkyne coupling 818 1326 with amines 526 and dihydroxylation 1009 and conversion of aldehydes to with cyclopropyl ketones 598 imidazoles 311, 920 keto esters 722 with epoxides and in enantioselective catalytic and electrophiles 607 organocuprates 572 hydrogenation 1515 and epoxide alcoholysis 496 with ketenes and aldehydes or N-heterocyclic carbenes as and Friedel-Crafts alkylation ketones 1261 stabilizing 275 648 with ketoximines 1326 P, π-dihydrobenzooxaphosphole and Fries rearrangement 675 with LiAlH4, reduction of 312 and halogens 643 esters 1580 phosphine 44 and hardness 359 with nitriles 672 phosphine-alkene, chiral 311 and hydroxylation of aromatic Lewis bases 357–359 phosphorus, and ionic liquids compounds 674 ab initio calculations, and base 311 and imino esters 672 strength 358 polymer-supported 566 and Johnson polyene and ionic liquids 395 rotaxane 311 cyclization 944 and nucleophiles 403, 459 TADDOL based 312 and organocopper reagents 555 and steric effects 366 light, and autoxidation 867 and oxonium ion formation 503 catalysts 1181 and optical activity 156 and reverse Friedel-Crafts catalyzed, Mukaiyama aldol circularly polarized 135 reactions 681 reaction 1181 and asymmetric synthesis and softness 359 definition 357 193 and solvent effects 371 with nucleophiles 575 plane polarized 133, 149 and steric effects 367 Lewis pairs, frustrated 1537, 1554 rotation of 134 and the periodic table 358, 365 as catalysts 311 LiHMDS 1174 and thioalkylation of aromatic conjugated alkenes 1530 limonylborane 935 compounds 671 Lewis structures 6, 15, 33 Lindlar catalyst, alkynes, and Lewis acids, as catalysts for and resonance 46 hydrogenation 1516 Curtius rearrangement benzene 38 catalytic hydrogenation 1516 1371 Ley reagent see TPAP Linear combination, MO 6 for transesterification 1233 LFER, linear free energy linear free energy relationship Lewis acids, as relay catalyst 311 relationship 383 (LFER) 383 carboxylic esters from ethers LHMDS (lithium linear polyacenes 61 502 hexamethyldisilazide) lipases, catalyst, and formation of catalysis, of hydroperoxide 369, 579–580 lactams 1243 rearrangement 1381 and aggregates 369 for dihydroxylation 1007 heteroatom Diels-Alder as a base 369 for ester hydrolysis 1220 reaction 1052 LiAlH4 see lithium aluminum for the aza-Michael reaction chiral 367 hydride 976 cleavage, of cyclic ethers 540 LiAlHSeH see lithium aluminum for transesterification 1233 of ethers 540 hydride, hydroselenide liquid chromatography see LC JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2032 SUBJECT INDEX

liquid crystals, catenanes and lithium, alkyl see organolithium by the Story synthesis 1332 rotaxanes 128 lithium, ammonia, reduction of crown ethers 119 liquid–liquid extraction, and flow aromatic compounds 1524 macrocyclic compounds, and reactions 336 reduction of aromatic catenanes 130 liquids, and ultrasound 332 compounds 1524 macrocyclic lactones, by ionic see ionic liquids lithium, and ultrasound 552 metathesis reactions 1430 literature searching 1630 arene 806 magnesium amides 703 and Journal of the Chemical in amines, reduction of aromatic magnesium dialkylcopper Society 1632 compounds 1526 reagents 1154 and SciFinder 1631 of aromatic rings 1526 magnesium diisopropylamide 722 online 1632–1633 in ammonia, and Birch magnesium enolate anions 1178 online, problems 1633 reduction 1524 magnesium halides, Grignard print 1630 with cyclopropanes 1530 reagents 245 specific problems 1631 ions, and ambident magnesium monoperoxyphthalate and Chemisches Zentralblatt nucleophiles 481 see MMPP 1632 metal, with alkyl halides 1134 magnesium, and the Barbier literature, annual reviews 1622 with Alkylidene oxetanes 1135 reaction 1130 irregular publications 1622 with gem-dihalides 1136 and the Grignard reaction 1130 journals 1608 LiTMP-butyllithium mixed coordination, Grignard reagent primary sources 1607 aggregates 1174 1132 secondary sources 1607, 1613 local aromaticity 64 coordination with heteroatoms lithiated allylic carbamates 1189 lone pairs, and bond angle 28 946 lithio-epoxide, rearrangement 523 lone pairs, electrons 28 dialkyl 1132 lithio-epoxides 1135 long bonds 26 formation of Grignard reagents lithioalkynes 551 long range rearrangements 1344 747 lithium (trimethylsi- loose transition state 406 magnetic anisotropy 55 lyl)diazomethane Lossen rearrangement 1338, 1372 and ESR 252 722 mechanism 1372 and NMR 19 lithium acetylide–ethylenediamine enantioselectivity 1372 magnetic field, and ESR 252 complex 1144 low-temperature matrix 73 and microwaves 334 lithium aluminum hydride see Lowest Unoccupied Molecular magnetic nonabeads, biocatalysts hydrides Orbital see LUMO 311 lithium aluminum hydride LTMP (lithium magnetic sequestering 569 hydroselenide, with hexamethyldisilazide) magnetic susceptibility isocyanates 1105 369, 579–580 anisotropies, arynes 774 lithium chloride carbenoids 730 and epoxides 523 magnetically recoverable catalyst lithium diethylamide 579 Luche reagent, reduction of 800 lithium diisopropylamide see aldehydes and ketones osmium catalysts 1008 LDA 1533 magnetically separable lithium hexamethyldisilazide see Luche reduction, aldehydes and nanoparticles 1503 LHMDS ketones 1533 and Friedel-Crafts acylation lithium hexamethyldisilazide 580 luiflavin 1521 662 lithium hydroxide, base 514 lumiflavin complex 1521 magnetite impregnated with lithium naphthalenide, with luminescence, and cucurbiturils iridium, catalyst 569 thioethers 884 132 maleic acid 178 lithium perchlorate see LUMO-HOMO interactions, and maleic anhydride, in the ene perchlorate radical cyclization 974 reaction 952 lithium perchlorate, and SN1 overlap 1046 malic acid, chlorination of 405 reactions 471 LUMO, and Diels-Alder reaction with PCl5 296 as Lewis acid 358 1036 malonaldehyde, enol hydrogen in ether, and formation of and tetraenes 45 bond 108 amino-alcohols 523 ethylene 10 malonate anions, coupling, Diels-Alder reactions 1039 of dienes 1393 palladium catalyzed 564 special salt effects 471 lyase and cyanohydrin formation malonates, and enantiotopic atoms lithium tetramethylpiperidide see 1210 183 LTMP lyonium ions, and solvent acidity malonic acids 184 and enolate anions 579–580 353 decarboxylation 751, 1236 lithium tri-sec-butylborohydride versus anhydride formation see Selectrides M effects for groups, table 377 1236 lithium triflate in acetonitrile, m-chloroperoxybenzoic acid see malonic ester synthesis 576 Diels-Alder reactions mCPBA and decarboxylation 576 1039 macrocage molecules 131 malonic esters, and Stobbe lithium-hydrogen exchange 806 macrocycles, and gyroscanes 132 condensation 1183 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2033

mandelic acid, and asymmetric addition of alkyl halides to acyloin condensation 1599 synthesis 164 alkenes 1004 addition, of alkanes to alkenes and resolution 169 addition of thiols to alkenes 939 manganese-porphyrin complexes 922 of thiols to alkenes 922 1017 addition, to cyclopropanes 906 addition–elimination 445, 720, manganese–salen complex, and addition to alkynes 911 776, 806 catalyst 1017 and alcohol addition to alkenes addition–elimination, manganese acetate, with alkenes 916 electrochemical 1026 and alkenes, with carboxylic substitution 695 manganese catalysts 311 acids 920 AdE2 (electrophilic addition, manganese complex, and and carbocation stability 902 bimolecular 892 dihydroxylation 1006 and Friedel-Crafts alkylation AdE3 895 manganese dioxide, and oxidation 651 AE +DE 607 of alcohols 1450 and halolactonization 999 alcohols, addition to alkenes and oxidation of amines 1462 and hydration of alkenes 913 916 oxidation of allylic and benzylic and hydrocarboxylation 984 from boranes 878 alcohols 1450 and oxymercuration 913 with alkenes 919 manganate esters 1006 and the Prins reaction 1214 with carboxylic acids 1231 manganese–salen complex, and and the Wacker process 1499 aldehyde or ketone asymmetric epoxidation hydrocarboxylation 983 rearrangement 1359 1017 hypohalous acids to alkenes aldehydes, hydride reduction manganese triacetate 949 997 1535 Mannich bases 1123 nitrosyl chloride with alkenes aldol condensation 1172 and amino leaving groups 466 1001 alkanes, cleavage 759 and coupling 567 radicals with cyclopropanes mechanisms, alkenes, addition, and elimination–addition 908 electrophilic 903 reactions 449, 466 masochistic steric effects 1066 dehydrohalogenation 1312 from ketones 1123 mass spectrometry see MS from boranes 1314 reaction with amines 520 and catenanes 130 halogenation 992 Mannich reaction 1123, 1211 and mechanism 296 hydroamination 925 and aminoalkylation 671 and tautomerism 96 metathesis 1425 and cyanohydrins 1211 high pressure, and SN2 with HOX 997 and Eschenmoser’s salt 1124 reactions 406 with singlet oxygen 870 and Robinson annulation methanonium ion 697 with sodium nitrite 1315 reaction 1179 radicals 251 mechanisms, alkyl halides and chiral auxiliary 1124 mass-law effect, and rate of Grignard reagents 553 Cinchona alkaloids 1124 reaction 412 allenes, by allylic diastereoselectivity 1124 matrix, argon 216 rearrangements 1320 enantioselectivity 1124 trapping 276 π-allyl complex 700 mechanism 1123 trapping carbenes 266 π-allyl palladium-complex metal catalysts 1125 maximum coordination number, reactions 564 organocatalysts 1124 and bonding 9 allylic radical halogenation 864 regioselectivity 1123 McFadden-Stevens reduction allylic-rearrangement 699 vinylogous 1125 1552 amides, from esters 1247 map, electron potential, ethylene diimide intermediate 1552 anchimeric assistance 422 10 McMurry coupling 1597 mechanisms, and alkylation of Marchantia polymorpha 1220 formation of unsymmetrical pyridine 880 Marcus equation 293 alkenes 1597 and benzynes 295 and base catalysis 356 intramolecular 1597 and bond cleavage 279 and Brønsted equation 356 mechanism 1597 and Brønsted equation 1288 Marcus theory 292 microwaves 1597 and catalysis 295 and mechanism 292 reagents 1597 and deuterium isotope effects and proton transfer 356 mCPBA (m-chloroperoxybenzoic 304 and rate constants 298 acid) 1010 and enols 305 and SN2 reaction 292 mechanical separation, and and flash photolysis 331 and Swain-Scott equation resolution 170 and frequency factor 303 462 mechanics, molecular see and half-life 301 Markovnikov addition, alkenes molecular mechanics and Hofmann rearrangement with HX 910 mechanics, wave 3 293 Markovnikov, anti see mechanisms 687 and intermediates 294 anti-Markovnikov A1 and A2, and acetal and IR 296 Markovnikov’s rule 902 hydrolysis 487 and isotope effects 304 acylation of alkenes 720 acetal and ketal formation 1102 and isotopic labeling 295 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2034 SUBJECT INDEX

mechanisms, and alkylation of benzoin condensation 1216 Cope elimination 1307 pyridine (Continued) benzyne 772, 777 Cope rearrangement 1411 and kinetics 296, 303 and isotope labeling 772 copper–quinoline and Marcus theory 292, 298 Grignard reagents, with aryl decarboxylation 684 and mass spectrometry 296 halides 805 Criegee, ozonolysis 1467 and Meerwein-Ponndorf-Verley reactivity order of halides Curtius rearrangement 1371 reduction 1539 773 cyclic 898 and NMR 302 biradical, Diels-Alder reaction intermediate 1464 and Oppenauer oxidation 1450 1045 and allylic cations 898 and oxidation–reduction 1441 Birch reduction of aromatic and electrophilic substitution and rate constant 297, 303 compounds 1525 695 and rate law 297 bis(decarboxylation) of diimide reduction of alkenes and rearrangement 446 dicarboxylic acids 1475 1521 and reduced mass 305 boranes alkylation 593 Prins reaction 1214 and secondary isotope effects oxidation 1385 reduction of hydrazones 306–307 with alkenes 736 1578 and solvent isotope effects 307 migration of boron 1368 [2+2]-cycloaddition 1059, and solvolysis 415 borderline 419 1062–1063 and stereochemistry 296 boron-to-carbon rearrangement reactions 1064 and steric hindrance 377 1385 [3+2]-cycloaddition 1031 and temperature 303 Boyland-Sims oxidation 674 of allylic carbanions 1034 and the Baylis-Hillman reaction bromination of acetone 304 cyclotrimerization of alkynes 1150 Buchwald-Hartwig Cross 1078 and the Neber rearrangement Coupling Reaction 787 cyclopropanes, addition 1369 mechanisms, C to N reactions 907 and vinyl halides 446 rearrangements 1369 ring opening 1358 and von Richter 293 Cannizzaro reaction 1601 cyclotrimerization, formation of and Walden inversion 296 carbamate hydrolysis 1224 triynes 1078 mechanisms, arenium ion carbanions 939 mechanisms, Dakin reaction 607–608 and elimination 1281 1473 and decarboxylation 683 carbenes, insertion 726 Dakin-West reaction 756 and reverse Gatterman-Koch with alkenes 1068 Darzens condensation 1190 reaction 683 carbenoids 1309 decarbonylation of acyl halides encounter complex 613 formation 1074 890 evidence for 609 carbocations 1309 with Wilkinson’s catalyst rate 610 addition of alkanes to alkenes 890 mechanisms, aromatic compounds, 939 dediazoniation, of alkylation 879 catalytic hydrogenation, aryldiazonium salts 1587 aromatic formylation 664 aldehydes and ketones definition 279 aromatic sulfonation 640 1536 dehalogenation, aryl halides aromatization by quinones chain, and alkene metathesis 1570 1443 1426 dehydration of alcohols 1300 arylamines with nitrous acid Chapman rearrangement 1435 dehydrohalogenation 1313 825 cheletropic reactions 1317 desulfurization 1589 arylation of alkenes 831 Chichibabin reaction 823 of aromatic rings 1589 arylation of arenediazonium chromium (VI) oxidation of determination of 293–308 salts 832 alcohols 1449 determining kinetic data 300 aryne see benzyne Chugaev reaction 1305 di-π-methane rearrangements A-SE2 893 cis-trans isomerization 294 1432 autoxidation 868 Claisen rearrangement 1411, diazotization of anilines 823 Bamberger rearrangement 836 1415 Diels-Alder reaction 1043 Bamford-Stevens reaction Claisen condensation, and electrophilicity– 1309 Dieckmann condensation nucleophilicity indices Barton reaction 1434 1255 1044 base induced elimination of cleavage of alkanes with dienone–phenol rearrangement sulfones 1310 superacids 759 1360 Bayer-Villiger rearrangement Clemmensen reduction 1579 diion, [2+2]-cycloaddition 1379 combination 282 reactions 1065–1066 Beckmann rearrangement concerted 1382 Diels-Alder reaction 1044 1376–1377 concerted, [2+2]-cycloaddition diketones, dianions 1256 benzidine rearrangement 1422 1059 dimer, and SNAr r reactions benzil-benzylic acid conducted tour 693, 699 770 rearrangement 1361 ion-pair 693 diol oxidative cleavage 1464 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2035

diradical 1059, 1411–1412 mechanisms, Gatterman method iodo azide to alkenes 1002 and photochemical 833 ion pair 418, 836 [2+2]-cycloaddition 1060 Gatterman reaction 666 and E1 reactions 1281 sigmatropic rearrangements gem-dihalides, from aldehydes ionic, alkenes, with 1406 or ketones 1128 trialkylsilanes and acids displacement, and Glaser reaction 877 1520 oxidation–reduction 1441 glycidic acid decarboxylation isocyanates with alcohols DMSO oxidation of alkyl 753 1105 halides 1490 Gomberg-Bachmann reaction with phosphine oxides 1260 Duff reaction 667 833 IUPAC nomenclature 398, 446 mechanisms, E1 reactions Grignard reaction 1133 and carbenes 468 1280–1281 Michael addition with and diazonium salts 467 and arenium ions 607 alkenes 963 mechanisms, ketones, acid E1anion reactions 1283 Grob fragmentation 1322 catalyzed rearrangement E1cB reactions 1281 Haller-Bauer reaction 759 1360 E2 reactions 893, 1274 haloacylation of alkenes 1005 by rearrangements of Eglinton reaction 877 haloform reaction 758 hydroperoxide 1380 Ei reactions 1297 halogenation of aldehydes and hydride reduction 1535 and Cope elimination 1307 ketones 706 mechanisms, lead tetraacetate, decarboxylation of esters halogenation of alkanes 859 cleavage of diols 1464 1304 Hay reaction 877 oxidation of alcohols 866 electrophilic 861, 913, 919 Heck reaction 812–813 oxidation of alcohols to cyclic addition 890 heterogenous hydrogenation ethers 866 halogenation of alkenes 1517 mechanisms, Lossen 993 Hoesch reaction 672 rearrangement 1372 elimination 1295 Hofmann elimination 1306 Mannich reaction 1123 elimination–addition 448 Hofmann rearrangement 1370 McMurry coupling 1597 and Mannich abases 466 Hofmann-Loffler¨ reaction 1433 Meisenheimer rearrangement at saturated carbon 449 homogeneous catalysts, 1383 at vinylic carbon 448 hydrogenation 1518 mercuric catalyzed hydration of enamine hydrolysis 1098 homologation of aldehydes or alkynes 916 ene reaction 952 ketones, with mechanisms, metal catalyzed epoxidation 1011 diazomethane 1366 acyloxylation 871 with sulfur ylids 1205 homolytic 280 coupling 562 conjugated carbonyls 1015 cleavage 1304 decarbonylation of aldehydes ester hydrolysis 1220–1223 Hunsdiecker reaction 887 889 Etard´ reaction 1479 hydration of aldehydes and hydrocarboxylation 984 Favorskii rearrangement 1362 ketones 1096 carbonylation 983 first-order reactions 297 hydroboration 933 metal hydride Fischer indole synthesis 1420 hydrocarboxylation 983 addition–elimination 699 Fischer-Hepp rearrangement hydrogen abstraction, and metal reduction of nitro 678 carbenes 727 compounds 1559 for oxidation of aldehydes to hydrogen exchange 697 methyl transfer 293 carboxylic acids 1495 hydrogenation of carbonyls mixed SN1-SN2 reactions 418 formamides, from isocyanides 1537 Neber rearrangement 1369 1264 hydrolysis, compounds 1098 Nef reaction 1099 formation of acyl cyanides of acyl halides 1218 mechanisms, neighboring group 1256 of alkyl halides 483 422 See also neighboring azoxy compounds from of amides 1225 groups oximes 762 of anhydrides 1218 and anti-dihydroxylation 1007 gem-dihalides from of carboxylic acid esters 384 and bromonium ions 423 aldehydes or ketones 1128 of hydroxamic acid 1099 and epoxides 424 Grignard reagents 748 of iminium ions 1098 and halonium ions 425 four-center 898 of nitro compounds 1099 and lactones 424 and hydroboration 933 hydroxy esters, by and rearrangement 423 fragmentation 1321 α-hydroxylation 1484 and solvolysis 424–425 free radical 280, 869 hydroxy ketones, by stereochemistry 423 addition 896–897 α-hydroxylation 1484 mechanisms, nitriles, from oximes Friedel-Crafts acylation identification of products 293 1326 660–661 interfacial 476 and fragmentation 1326 Friedel-Crafts alkylation, intramolecular rearrangement and rearrangement 1326 reversal 682 682 mechanisms, nitrogen extrusion Fries rearrangement 676 inverse isotope effects 305 reactions 1330 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2036 SUBJECT INDEX

mechanisms, nitrosation of and pinacol coupling 1595 mechanisms, selenium dioxide amines 761 and quantum yield 331 allylic oxidation of alkenes of ketones 710 pinacol rearrangement 1354 1482 mechanisms, non-concerted, and Prevost reaction 1007 α-oxidation of ketones, benzidine rearrangement Prins reaction 1213 mechanism 1487 1424 proton-transfer reactions 350 mechanisms, semibenzilic 1363 nonsynchronous, Pshcorr reaction 833 mechanisms, SET 420 [3+2]-cycloaddition 1031 Pummerer rearrangement 1603 and aldol condensation 1171 nucleophilic 895, 900, 1353 pyrolysis 1297 and alkyl halides 1569 mechanisms, nucleophilic of homoallylic alcohols 1328 and chain reactions 420 aromatic substitution 768, quinones 446 and CIDNP 421 770 mechanisms, radical 839, 865, and coupling 567 nucleophilic rearrangements 868, 1475 and ESR 421 1336 addition of alkanes to alkenes and oxidation–reduction 1441 of formation, organolithium 939 and radical cyclization 421 reagents 751 alkylation of aromatic and radical probes 421 of ozonolysis of alkenes 1467 compounds 879 and substitution reactions of substitution reactions 404 and halogenation of alkenes 452 of the Kolbe reaction 885 995 formation of Grignard reagents of the Pauson-Khand reaction and SRN1 reactions 775 748 987 arylation of aromatic organocalcium 249 of the Stevens rearrangement compounds 879 versus SN2 reactions 421 1381 chain 1475 mechanisms, Shapiro reaction of the Wacker process 1499 chain, and SRN1 reactions 775 1309 Oppenauer oxidation 1450 cyclization 971 Sharpless asymmetric organolithium reactions 1135 Diels-Alder reaction 1044 dihydroxylation 1008 organometallics and alkyl halogenation of allylic Sharpless asymmetric halides 559 hydrogen 864 epoxidation 1017 conjugate addition 963 hydroboration 740 [3s, 5s]-sigmatropic shifts mechanisms, of anilines with pairs 1384 1406 Caro’s acid 1502 reaction with cyclopropanes Simmons-Smith reaction of aromatic side chains 1473 908 1075 of aromatics to phenols 866 SH1andSH2 reactions 845 Simonini reaction 887 of cathecols and hydroquinones with aromatic compounds 845 six-center 898 1460 mechanisms, Ramberg-Backlund¨ and decarboxylation 752 of thiols to disulfides 1510 reaction 1317 SN1 reactions 410 oxidation and reduction 1439 Raney nickel desulfurization acyl halides with alcohols oxidation, of amines to amine 1589 1227 oxides 1504 reaction of organocuprates 556 amination of alkanes 526 of thioethers 1507 rearrangements, σ-bond, metal and deuterium 456 mechanisms, oxidative cleavage of catalyzed 1431 and ion pairs 414 alkenes 1471 reduction of carbonyls with and primary carbocations mechanisms, oxidative sodium in ethanol 1537 451 decarboxylation of of diazonium salts with and secondary isotope effects carboxylic acids 1474 sodium sulfite 1566 456 oxygen insertion, hydrocarbons of hydrazones 1578 hydrolysis of acetals 486 1477 and Grignard reactions 1132 SN1cA reactions 467 ozonolysis 1467 Reed reaction 872 SN1cB reactions 468, 527 Paal-Knorr pyrrole synthesis reverse Friedel-Crafts SN2 reactions 404–409 1114 alkylation 682 acyl halides with alcohols Passerini reaction 1265 Sandmeyer reaction 827 1226 pericyclic 280, 869, 912 Schmidt reaction 1374 and deuterium 456 Prins reaction 1214 SE1 reactions 613, 687, 691 and diol formation 1007 pyrolysis of homoallylic decarboxylation 755, 757 and hydrolysis of acyl alcohols 1328 SE2 reactions 608, 687 halides 1218 periodic acid with diols 1464 SE2 (co-ord) reactions 690 and secondary isotope effects Petasis alkenylation 1202 decarboxylation 755 456 Peterson alkenylation 1192 SEAr reactions 608, 687 sulfonyl sulfur, nucleophilic photochemical 330 mechanism 628 substitution 1266 actinometer 331 SEC reactions 690 SN2′ reactions 442 and emission 331 second-order reactions 297 SN2cA reactions 468 and fluorescence 331 SEi reactions 688 SNAr reactions 608, 768 and phosphorescence 331 SEi′ reactions 694 SNi reactions 440, 443 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2037

mechanisms, solvolysis of alkyl von Richter reaction 295 memory effect 1343 halides 306 von Richter rearrangement 834 of migrating groups, Sommelet-Hauser Wacker process 1500 rearrangements 1342 rearrangement 835 Wagner Meerwein Menshutkin reaction 408, 513 SRN′ reactions, arylation, active rearrangement 1353 and SN2 reactions 408 methylene compounds Walden inversion 405 mercaptides, as reducing agents 819 Wallach rearrangement 1436 1588 SRN1 774 Wilkinson’s catalyst, Merck Index 1620 arylation of active methylene hydrogenation 1518 mercuric acetate, and compounds 820 Willgerodt reaction 1605 acyloxylation 871 SRN2 reactions 776 Wittig reaction 1196 and oxymercuration 913 Stevens rearrangement Wittig rearrangement 1384 dehydrogenation of amines 1381–1382 Wolff rearrangement 1364 1445 Stille coupling 718 Wolff-Kishner reduction 1578 with alkenes 913 substitution, IUPAC 465 Wurtz reaction 549 mercuric chloride, and orbitals 8 sulfonyl sulfur, nucleophilic mechanochemistry 338 linear 8 substitution 1266 and chlorination of mercuric compounds, the sulfoxide elimination 1310 hydrocarbons 338 Corey-Seebach procedure sulfur ylids 1205 and metal catalyzed reactions 1110 Suzuki-Miyaura coupling 802 338 mercuric oxide, oxidation of symbols for IUPAC and ozone 338 glyceraldehyde 148 nomenclature 399–400 mechanophore, β-lactams 1263 mercuric salts, and hydration of termolecular addition 893 Mechanosynthesis 1244 alkynes 914 mechanisms, tetrahedral 445, medium size rings, and I strain complex with alkynes 916 1088 379 mercury compounds, substitution isolation of intermediates 1091 strain 215 690 acyl halides with alcohols 1227 medium, and rate of reaction 390 mercury, sp orbitals 8 amines with anhydrides 1240 and reactivity 390 Merrifield synthesis 1244 and conformation 1092 Diels-Alder in water 391 meso compounds 137 and formation of aziridines 447 effects, on acids and bases 370 and diastereomers 158 and hyperconjugation 447 supercritical carbon dioxide and monocyclic compounds and isotope labeling 1090 392 180 and leaving groups 1093 water 391 definition 159 and MO calculations 447 Meerwein arylation 830 meso-epoxides 1359 and radical addition to alkenes Meerwein-Eschenmoser Claisen mesoionic compounds, and 847 rearrangement, Claisen aromaticity 89 and substituent effects 455 rearrangement 1417 mesomeric effect 48 See also and vinyl halides 446 Meerwein-Ponndorf-Verley resonance directionality 1092 reduction, aluminum free mesylates 465 evidence for 1090 1539 leaving groups 465 hydrogen ion catalyst 1090 and alumina 1539 mesyltriflone 1317 in acid solution 1090 and microwaves 1539 meta selectivity, and aryl radicals kinetics 1090 and Oppenauer Oxidation 1450 854 mechanism 1089 cyclic transition state 1539 meta substitution 615–616 position of equilibrium 1093 enantioselectivity 1539 metal carbonyls and rate constant 1090 mechanism 1539 sonochemistry 333 reversibility 1094 of carbonyls 1538 metal catalyzed see catalysts special detection of transition state 1539 acyl halides with alcohols 1227 intermediates 1092 Meinwald rearrangement 1355 acyloxylation of hydrocarbons stereoelectronic control 1092 metal catalyst 1355 871 synthetic transformations 1094 Meisenheimer rearrangement acyloxylation, mechanism 871 types 1094 1383 metal catalyzed, addition of mechanisms, thermal elimination mechanism 1383 alcohols to alkenes 918 of sulfoxides 1311 Meisenheimer salts 769 of aldehydes to alkenes 981 transesterification 1233 and NMR 769 of alkynes to alkenes 942 trapping intermediates 295 and X-ray crystallography 769 alkanes to alkenes 940 types 279 Meisenheimer-Jackson salts 769 alkenes to alkenes 942 vinylboranes, with NaOH and Meldrum’s acid 807 metal catalyzed, alcohols, allylic, iodide to give alkenes and acidity 368 oxidation 1449 1388 and conformation 368 coupling 568 vinylcyclopropane melting points, and Beilstein 1618 from carboxylic acids rearrangement 1407 and hydrogen bonding 110 1546–1547 von Braun reaction 544 MEM ethers 492 with alkenes 917 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2038 SUBJECT INDEX

metal catalyzed, alcohols, allylic, and Claisen condensation 1183 carbon dioxide, with oxidation (Continued) and dehalogenation of acyl organoboronates 1161 with anhydrides 1228 halides to ketenes 1320 carbon monoxide, aryl halides with carboxylic acids 1229 and diamination 1021 and aryl iodonium metal catalyzed, aldehydes, with and elimination of dihalides to compounds 670 alkenes 981 alkenes 1319 and phenylboronic 670 metal catalyzed, alkenes, and enols, preformed 1176 carbonylation 605, 982 carbonylation 984 and forbidden electrocyclic of alkyl halides 604 coupling 945 reactions 1396 of amines 764 isomerization 909 and Hiyama coupling 546 of aryl halides 670, 821 metathesis 1426 and hydrogenation 1513 carboxylation 606 to alkenes 945 and hydrosilation of conjugated of alkenes 988 with alcohols 917 alkenes 1528 carboxylic acids, reduction with with radicals 970 and mechanochemistry 338 borane 1547 Metal catalyzed, alkoxides with and Meinwald rearrangement with alkenes 920 aryl halides 782 1355 carboxylic esters 1548 alkoxysilanes with aldehydes and nitrenes 1024 metal catalyzed, catalytic 1105 and oxidation of alkenes to hydrogenation, aldehydes alkyl halides with alkenes aldehydes or ketones 1499 and ketones 1536 1004 and reductive coupling to diols chiral 1053 from carboxylic acids 1238 1594 Claisen rearrangement 1416 alkylation of amides 528 and Suzuki-Miyara coupling cleavage, of benzofurans 571 of ester enolate 584 593–594 conjugate addition, of pyridine 880 and the Barbier reaction 1130 organolithium reagents alkyne anions, with aldehydes and the Boord reaction 1321 979 and ketones 1143 and the Grignard reaction trifluoroborates 969 with aldehydes and ketones 1130–1131 Cope rearrangement 1410 1144 and the Michael reaction 955 coupling 564 alkynes, alkylation 597 and the Ritter reaction 1258 alkenes to alkenes 945 coupling 945 and Wacker process 1499 alkyl halides 562 hydrogenation 1516 and α-hydroxylation of ketones aryl halides 562 oxidation to diketones, metal 1483 Grignard reagents 881 catalysts 1501 metal catalyzed, anhydrides from mechanism 562 tetramerization 1076 acyl halides with organometallics 558–563 trimerization 1076 carboxylic acid salts 1235 with silanes 545 with acyl halides 1156 aromatic halogenation 644 cyanation 723 with aryl halides 950 aryl halides and carbon dioxide cyclization of diynes 943 amidation of alkenes 930 667 of en-ynes 985 amides, from carboxylic acids arylation, of alkenes, the Heck [2+2]-cycloaddition 1057, 1242 reaction 811 1059 amination 518, 636, 741–742 of amines 786–787 forbidden 1396 of alkenes 924–925 of silanes 822 [2+2+2]-cycloaddition 1081, of aromatic compounds arylboronic acids with alkenes 1083 635–636 803 [3+2]-cycloaddition 1032 amine arylation 788 coupling with arylmetallic intramolecular 1034 amines to nitriles 1126 808–809 cyclopropanation 1073 with aldehyde or ketones asymmetric hydrogen transfer alkenes 1071 1112 1544 metal catalyzed, cyclopropyl ring with alkynes 927 Baeyer-Villiger rearrangement opening 599 with epoxides 522 1378 cyclotrimerization, triynes with esters 1246 boranes, alkylation 593 1078 and acetal formation 1101 conjugate addition 967 decarbonylation, of acyl halides and alcohol dehydration 1300 with aldehydes 1146 to alkenes 1315 and alkyne coupling 878 boronates, with imines 1165 decarboxylation 754 and aromatic formylation 664 boronic acids, alkene coupling decarboxylative addition 887 and aromatization 1443 803 decarboxylative coupling and aryl halides, Kumada with aldehydes 1146 alkynyl acids 888 coupling 807 with imines 1165 dehalogenation of acyl halides and aza-Michael reaction 976 with nitriles 1169 to ketenes 1320 and Baeyer-Villiger boronic esters with aldehydes dehydration of alcohols 1300 rearrangement 1378 1147 dehydrohalogenation 1312 and catalytic dehydrogenation borylation 792 diazoacetates with alkenes 1454 carbenes 1070–1071 1022 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2039

diazoalkanes, and hydrogen exchange, aromatic sulfides oxidation to sulfones cyclopropanation 1068 compounds 630 1506–1508 elimination of halo ethers to metal catalyzed, hydrogenation sulfonation of aromatic alkenes 1320 1515 compounds 641 enamines, from amines 1446 of amides 1583 Suzuki-Miyaura coupling 801 ene reaction 952 of imines 1554 thio-Michael addition 978 carbonyl- 954 catalytic, cyclopropanes 1530 thiols with aryl halides 783 enol esters from alkynes 920 reduction of nitriles 1556 transamidation 1237 enol ether reactions 581 hydrosilation of alkynes 941 transfer hydrogenation 1520 enolate anions 583, 1175 anti-Markovnikov selectivity transition, and ether formation epoxidation 1011–1012 940 491 epoxides, and amines 523 imines, from amines 1461 vinylcyclopropane with cyanides 601 with diazo compounds 1167 rearrangement 1407–1408 esterification of aldehydes with intramolecular, metal catalyzed, with alcohols 1497 alkoxymercuration 917 1-haloalkynes 598 esters from alkyl halides 605 isomerization of alkenes 909 with acyl halides 1315 Finkelstein reaction 534 of allylic acetates 1367 with esters and base 1254 metal catalyzed, for addition of of allylic alcohols 1367 with Grignard reagents 553 silanes to alkenes 940 of propargyl alcohols 1368 with organolithium reagents for carbonylation 982 ketones, from epoxides, metal 948 enantioselective 982 catalysts 1355 with the Reformatsky reaction mechanism 983 Knoevenagel reaction 1187 1152 for carboxylation of alkenes lactones from alkenes 988 metal cations, and crown ethers 988 from epoxides 1359 117 for catalytic dehydrogenation of Mannich reactions 1125 metal complexes see complexes alcohols 1454 Meyer-Schuster rearrangement and atropisomers 143 for dehydration of oximes to 1368 and diazoalkanes 1070 nitriles 1325 Michael addition 957, 960 cyclobutadiene 74 for dehydrogenation 1445 alkynes 966 metal compounds, reaction with for hydroboration 936 Mukaiyama aldol reaction alkenes 946 for hydroformylation 989 1181–1182 metal cyanides see cyanides for oxidation of alcohols with Nazarov cyclization 958 metal free, biaryl synthesis 800 TEMPO 1452 nitrenes, insertion 715 semihydrogenation 1517 for pinacol coupling 1594 [1,3]-O→C rearrangement metal halides, diazotization 543 for transesterification 1233 1405 transmetalation 744 metal catalyzed, formation of aryl Oppenauer oxidation 1450 metal hydrides 1534 nitriles 673 organolanthanides 1021 addition to alkenes 938 formation of silyl enol ethers oxidation 1477–1478 addition–elimination, 721 of hydrocarbons with mechanism 699 metal catalyzed, Friedel-Crafts hydroperoxides 870 and reduction of alkynes 1522 alkylation 650 oxidative decarboxylation 1474 reduction of aldehydes and Fries rearrangement 676 metal catalyzed, Pauson-Khand ketones 1533 Grignard reagents coupling 880 reaction 987 metal ions, and crown ethers 117 ultrasound 1163 phenols, from aryl halides 781 and HSAB 361 with imines 1163 preparation of aryl nitriles 794 and SN1 reactions 471 halides, aryl, coupling with of boronates 792 catalyst, esters, hydrolysis 1219 arylmetallic 808–809 Prins reaction 1215 metal mediated, acylation of heteroaryl, hydrogenation radical cyclization 974 amines 1239 1570 radical halogenation 864 addition, HCN to alkynes 991 Henry reaction 1186 rearrangement of vinyl and decarboxylation 683 heteroatom Diels-Alder epoxides 1355 and the Baylis-Hillman reaction reaction 1053 cyclopropylcarbinyl 1357 1151 hydration of alkenes 913 formation of allenes 1319 carbonylation of alkyl halides hydration of alkynes 914–915 reduction of conjugated alkenes 603 hydride reagents, reduction of 1527 coupling, alkyl halides 550 nitriles 1556 reductive amination 1119–1120 deoxygenation of hydroamination 929 Scholl reaction 657 bis(alkoxides) 1315 intramolecular 926 σ-bond rearrangement 1431 halogenation 861 of alkenes 1020 mechanism 1431 of ketones 705 hydrocarboxylation, silanes, reduction of aldehydes rearrangement, aniline mechanisms 984 or ketones 1540 ammonium salts 680 hydroformylation 989 Sonogashira coupling 817 metal oxides, and hydrogenation of alkynes 990 Stephens–Castro coupling 817 1513 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2040 SUBJECT INDEX

metal reduction, of sulfonyl and reduction with silanes 1541 cross 1429 halides 1270 and Reformatsky reaction 1152 alkynes 1430 metal salts, formation of acylals carbenes 726 domino 1429 1104 dimerization of alkenes 942 double 1429 formation of dithioacetals and dissolving metal reductions homo- 1429 dithioketals 1108 1524 ring closing 1424, 1431 metal-alkene complex 1517 electromotive series 744 tandem 1429 metal–carbene complex 1426 exchange 554 triple 1429–1430 metal-halogen exchange 750, for alkene metathesis 1425 vinylcyclopropane–alkyne 1134 for oxidation of alcohols 1430 metal–salen complexes, and 1455–1458 with dienes 1430 epoxidation 1017 in acid and reduction of nitro methane hydrate 124 catalysts 1017 compounds 1559 methane, and PES 12–15 metal, acetates, and in amines, reduction of aromatic bond angles 9 dihydroxylation of alkenes compounds 1526 bond energy 30 1009 in ammonia, and Birch chlorination 293 metal, carbene complexes, and reduction 1524 from bromomethane 1440 olefination 1203 and decyanation 760 PES 14 with esters 1203 reduction of alkynes 1522 radical cation 15 with lactones 1203 phase transfer catalysts, chiral radical, electronic structure 17 metalated alkynes 597 597 spectroscopy 12 metalated aryls, formation of powdered 748 methanoannulenes 79–80 biaryls 657 metals, reduction of aldehydes and and antiaromaticity 86 metalated imines 1265 ketones 1537 methanoazaannulene 79 synthetic applications 1266 of alkyl halides 1568 methanol, as a guest 124 metalations, aromatic compounds of azides 1564 from bromomethane 1440 675 of heterocycles 1526 methanonium ion 224, 697 metalations, directed 732 of nitro compounds, IR and mass spectrum 697 metalations, directed ortho 552, mechanism 1559 Methods in Organic Synthesis 806 metals, surface area, and the 1625 metalations, of C—H 730 acyloin condensation methoxide, potassium, and metalations, with organometallic 1599 phenalene 61 reagents 730 surface phenomena, α-methoxy-α- metallocenes 66, 116 hydrogenation 1517 trifluoromethylphenyl and a chiral axis 152 transition, promotion of radical acetic acid (MTPA) see and aromatic substitution 66 reactions 853 Mosher’s acid and chirality 145 transmetalation 744 methoxyamines, from haloamines and cyclopentadiene 66 used, aldehydes or ketones, with 1378 and 18-electron systems 67 organometallics from organolithium reagents and transmetalation 744 1136–1142 741 bonding 66, 116 vapor form 748 with Grignard reagents 741 multi-decker 66 with aldehydes, formation of with organometallics 740 metallocycles 89 acyl radicals 842 methoxycarbonylsulfamoyl metalloenzyme, artificial, alkene with boranes 967 triethylammonium metathesis 1428 with crown ethers, and hydroxide see Burgess metalloids 734 decyanation 760 reagent metals, alkali, and radical ions with imines 1262 methoxymethyl carbocation 230 265 metathesis, alkenes 1424 See also methoxyvinyllithium, with allylic silanes with aldehydes alkene metathesis aldehydes or ketones 1189 1148 and molybdenum catalysts 1-methyl-2-chloropyridinium ammonia, reduction of aromatic 1426 iodide see Mukaiyama compounds 1524 and ruthenium catalysts 1426 reagent and acid, deoxygenation of and stability of alkenes 1425 methyl anions 243 aldehydes or ketones 1577 equilibrium 1425 methyl aromatic compounds, and reduction of anhydrides 1580 formation of cyclic dienes 1430 Etard´ reaction 1479 and alcohols, with alkenes functional group compatibility α-CH oxidation to aldehydes 1520 1430 1478 and ammonia, decyanation of mechanism 1425 methyl carbocations, X-ray of nitriles 760 structural changes in the 224 and conjugate addition of reaction 1425 methyl compounds, from amines 976 synthetic variations 1430 carboxylic esters 1583 and elimination of halo ethers to metathesis, alkynes 1430 reduction of carboxylic esters alkenes 1320 and formation of lactones 1430 1583 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2041

methyl groups, neighboring group and metal catalysts 955 and keto-enol tautomerism 702 participation 438 and organocatalysts 955 principle of 1215 methyl ketones see ketones and organocuprates 960 microwave irradiation 334–336 methyl radicals, ESR 258–259 and radicals 956 alcohols, oxidation to polarity 853 and silyl enol ether 956 carboxylic acids 1492 methyl sulfate, with and silyl enol ether, alcoholysis of anhydrides 1228 alkynyltrialkylborates diastereoselectivity 956 aldehyde conjugate addition 1389 and sulfur ylids 1206 979 methyl transfer 293 and tautomerism 103 alkoxides with aryl halides 781 methylarenes, photooxidation and ultrasound 955 alkyl halides from tosylates 536 1480 aza- 975 See also aza-Michael alkynes, conversion to vinyl methylation, of aryldiazonium enantioselective 976 halides 912 salts 829 green 976 amides to isocyanides 1328 methylcyclohexyl cations 232 metal catalyzed 976 amines with esters 1246 methylene compounds, active see organocatalysts 976 acylation 1240 active methylene chiral catalysts 960 microwave irradiation, and acetal compounds chiral phase transfer catalysts formation 1103 acidity 364 956 and acetal hydrolysis 488 by reduction of ketones 1577 conjugated substrates 954 and acylation of amines 1241 CH oxidation to amines 1486 cyanide ion 958 and aldehydes to nitriles 1118 methylene-pentadiene see diastereoselectivity 959 and alkylation of lactams 478 dendralenes double 977 and amination 516 methylene, by desulfurization enantioselectivity 955, 960 aromatic compounds 635 1589 enolate anions 1179 of ketones 714 methylene, carbene 266, 269 formation of enolate anions and amines 513 singlet 272 895, 955 and aminocarbonylation 669 from diazomethane 726 Grignard reagents 1159 and anhydride formation 1236 insertion 725 intramolecular 957–958 and biaryl formation 805 oxidation 1477 metal catalyzed 957, 960 and Claisen condensation 334 methylenecyclopentanes 1034 organocatalysts 956, 960 and conjugate addition 976 methylenecyclopropanes, with conjugated aldehydes of aldehydes 979 rearrangement 1357 963 and decarboxylation 753 methylids, sulfur 1204 organolithium reagents 1159 and dehydration of amides to methylimidazole, solvent 354 organometallic reagents nitriles 1327 methylimidazolium ions, ionic 964–965, 1159 and dehydration of oximes to liquids 393 and NMR 964–965 nitriles 1325 methyllithium 165, 245 enantioselective 964–965 and dielectric heating 334–335 X-ray crystallography 245 phospha- 977 and Diels-Alder reaction 334 methylmercaptide, as a reducing enantioselective 977 and Doebner modification 1188 agent 1588 phosphine catalysts 956 and Ehrlich-Sachs reaction methylpyrrole, solvent 354 stereoselectivity 896 1169 methylrhenium trioxide, and substrates for 954 and enamines 587 alcohol dehydration 495 sulfur ylids 1206 and ester formation 499 methylsulfonyl carbanion 1255 to conjugated alkenes 954 and ether formation 491 Methyltrioxorhenium 1204 vinylogous 957 and formation of Meyer-Schuster rearrangement water promoted 956 amino-alcohols 522 444, 1367 with alkynes 957 and Friedel-Crafts acylation metal catalyzed 1368 with organocatalysts 959 659 Meyers synthesis 591 with vinyl sulfones 959 microwave irradiation, and Fries micellar catalysis, and Williamson Michael type, alkenes, rearrangement 676 ether synthesis 490 [2+2]-cycloaddition 1058 and Gibbs energy 335 Michael acceptors, N-heterocyclic mechanism, and epoxidation and Grignard reagents 1129 carbene catalyzed 1016 and heteroaryl coupling 658 umpolung 957 substrates 912, 954, 991 and Huang-Minlon Michael addition 895, 898 reactions 896 modification 1577 and chiral phase transfer 956 microchemistry 336 and hydride reduction 1533 and DABCO 958 microencapsulated, OsO4 1009 and hydrolysis of C=N and electrochemistry 956 microfiche 1609 compounds 1097 and enamines 587 microfilm 1609 and hydrolysis of nitriles 1100 and enzymes 960 microreactors technology 336 and hypervalent iodine and genomic salmon testes ionic liquid droplet 338 oxidation of alcohols 1454 DNA 955 microscopic reversibility 291, and inorganic esters 504 and ionic liquids 956 1095 and ionic liquids 395 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2042 SUBJECT INDEX

microwave irradiation, and Fries epoxides and ammonium rearrangements, memory rearrangement (Continued) hydroxide 522 effects 1342 and ketal hydrolysis 488 and HX 541 stereochemistry, in and β-lactams 1263 ester hydrolysis 1220 rearrangements 1340 and Meerwein-Ponndorf-Verley ethers with alkynes 939 in rearrangement 1335 reduction 1539 formation of acylals 1104 migrations see rearrangements and microwave ovens 334 of enamines 1112 alkene, and hydroboration 700 and Mitsunobu reagents 500 of imines 1112 alkene, in hydration of alkynes and Montmorillonite clay 478 Friedel-Crafts acylation 659, 915 and α-oxidation of ketones to 662 alkyl, from borate ate complex diketones 1487 Friedel-Crafts alkylation 650 736 and phase transfer catalysis Friedlander¨ quinoline synthesis and reverse Friedel-Crafts 477 1113 alkylation 681 and phosphine reactions with Fries-rearrangement 676 and the ipso carbon 633 alkyl halides 1194 halides, aryl, halide exchange antarafacial 1401 and polarization 334 791 arylazo group 679 and rate acceleration 335 halogenation of alcohols 538 boranes, sterochemistry 1386 and rate enhancement 334 halogenation of ketones 704 origin, and rearrangement and rate of reaction 478 Heck reaction 335 1335 and reactivity 477 Hunsdiecker reaction 886 [2,3]-oxygen-to-sulfur 1422 and reduction of nitro hydrosilation, of imines 1554 para, and Fries rearrangement compounds 1560 Knoevenagel reaction 1187 676 and Sonogashira coupling 817 magnetic field component 334 photochemical, alkenes 699 and Stephens–Castro coupling McMurry coupling 1597 suprafacial 1401–1402 817 metal catalysts, preparation of [1,3]-suprafacial, and Stille coupling 717 aryl nitriles 794 photochemistry 1406 and superheating 334 Mitsunobu reaction 336 terminus, and rearrangement and synthesis 335 microwave irradiation, origins 1335 and the Baylis-Hillman reaction 334 migratory aptitudes, and the 1150 oxidation of alcohols 1458 pinacol rearrangement and the Beckmann of thiols 1509–1510 1354 rearrangement 1375 Pauson-Khand reaction 986 Curtius rearrangement 1340 and the Fischer indole synthesis Pechmann condensation 654 Hofmann rearrangement 1340 1419 phenols, from aryl halides 780 in hydroperoxide and the Heck reactions 812 reaction of thiols and alcohols rearrangement 1381 and the Krohnke¨ reaction 1491 507 in rearrangements 1340 and the Ritter reaction 1258 reactors 335 in the Baeyer-Villiger and the Schmidt reaction 1117 reduction of esters to alcohols rearrangement 1379 and the Williamson reactions 1548 in the Beckmann rearrangement 491 Sonogashira coupling 335, 818 1376 and the Wittig reaction 1196 Stephens–Castro coupling 818 in the Schmidt reaction 1373 and thioamide formation 1238 sulfonation of aromatic in the Stevens rearrangement and warming 334 compounds 641 1381 microwave irradiation, aryl halides Suzuki reaction 335 in the Wittig rearrangement with amines 786 synthesis of biaryls 798 1384 aryl triflates with amines 786 thermal effects 334 ketones, by rearrangements of benzylic halides from alcohols Ullmann reaction 335 hydroperoxide 1381 478 wavelength 335 radicals 1348 Buchwald-Hartwig Cross microwave ovens, and microwave rearrangements, H versus alkyl Coupling Reaction 787 chemistry 334 versus aryl 1341 carbonylation of aryl halides microwave reactors 335 Sommelet-Hauser 821 microwave spectroscopy, and bond rearrangement 1383 conversion of carboxylic acid to distance 24 milling, and reactions 338 amides 1242 and conformations 188 milling, ball see ball milling CuCN and aryl halides 794 Fries rearrangement 677 Mills reaction 829 cycloaddition reaction 336 microwave-assisted flow reactions Mills-Nixon effect 51 Dieckmann condensation 1254 337 and electrophilic aromatic dihydroxylation reaction 336 migrating groups, and retention of substitution 625 dry-reaction 334–335 configuration 1338 mirror images, superimposable electric field component 334 hydrogen, in rearrangements 137 electromagnetic waves 334 1339 mirror plane, and allenes 144 ene reactions 334 in radicals, rearrangements miscellaneous reagents, epoxidation 1011 1348 conjugated alkenes 1529 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2043

Mislow-Evans rearrangement and the tetrahedral mechanism molecular necklaces 128 1422 447 molecular orbitals see MO Mitsunobu cyclodehydration 500 antarafacial shift 1401 molybdenum, catalysts, and Mitsunobu reaction 499 antiaromaticity 71 metathesis 1426 alcohols, with carboxylic acids basis sets 1048 molybdenum peroxide, 1230 benzene 35 α-hydroxylation of ester and alcohols dehydration 495 CNDO 36 enolate anions 1483 and amination 519 cyclobutadiene 73 α-hydroxylation of ketone and ether formation 495 dipole moments 36 enolate anions 1483 and microwaves 336, 500 energy barrier to rotation 190 molecular sieves, and amine and Williamson ether synthesis MINDO 36 formation 514 490 Monte Carlo 37 and epoxidation 1017 azide and epoxides 523 Monte Carlo methods 37 and formation of imines 1113 esterification 500 nitrogen 14 and Jones reagent 1447 formation of alkyl azides from PM3 36 as a dehydrating agent 1229 alcohols 1374 semiempirical 36 molecular, propellers, and a chiral formation of amines 517 suprafacial shift 1401 axis 152 polymer supported 500 energies 58 recognition 121 Mitsunobu reagents, recyclable theory, activation hardness 625 refraction, and aromaticity 64 500 and electrophilic aromatic and hardness 64 mixed benzoin condensation substitution 625 ribbons 128 1217 and resonance 34 rotors 130 mixed Claisen condensation see and cyclopropyl cation ring shuttle 130 Claisen opening 1397 stators 130 Mixed organocuprates 556, 961 and ferrocene 67 stoppers, fullerenes 131 mixed SN1-SN2 reactions 418 butadiene 40 switches 128 Mizoroki-Heck reaction see Heck Mobius¨ aromaticity 88–89 threads 128 MM3, and molecular mechanics double-twist 1049 turnstiles 130 205 Mobius¨ strip 89, 1049 molecularity, and rate law 298 MM4 205 compounds, and chirality 147 molecules, chiral 133 calculations, and ligand exchange, and rotaxanes molecules, strained see strained hyperconjugation 95 128 molecules and molecular mechanics 205 Mobius-H¨ uckel¨ method 1393, MOM ethers 492 MMFF 205 1401, 1403, 1414 monochloroborane 933–934 and molecular mechanics 205 and cyclopropane ring opening monohapto compounds 115 MMPP (magnesium 1358 monooxygenases 1507 monoperoxyphthalate) and electrocyclic reactions monoperoxysulfate, oxidation of 1011 1391 alcohols 1456 and oxidation of hydrazones and orbital symmetry 1396 Monte Carlo methods 37 1462 Diels-Alder reaction 1045 Montmorillonite clay 504 MO calculations 4–6, 34 modified neglect of diatomic and acetal cleavage 488 ab initio 36 overlap 36 and acylation of amines 1241 AM1 36 Moffatt oxidation, and DMSO and addition of thiols to alkenes and [1,5-]-phenyl migration 1451 922 1405 of alcohols 1451 and Hofmann rearrangement and aromatic compounds 35 molar rotation, definition 136 1371 and azulene 67 molecular belts 128 and microwaves 478 and bond angles 36 molecular cage macrocycles, and with alcohols and aziridines and bond distances 36 flow chemistry 337 574 and conformation 368 molecular catalysts 310 Montmorillonite K-10 1504 and cross conjugation 44 molecular conformation, and Pechmann condensation and cyclobutadienes 73 geometry 205 654 and cyclopropane 208 molecular electrostatic potentials, MoOPH, α-hydroxylation of ester and free energy for SN2 409 alkene reactivity 903 enolate anions 1483 and fullerenes 91 molecular knots 130, 132, 147 α-hydroxylation of ketone and Huckel’s¨ rule 71 and DNA 131 enolate anions 1483 and hybridization 9 and metals 131 Morita-Baylis-Hillman see and ion pair formation 417 molecular mechanics 204–206 Baylis-Hillman reaction and naphthalene 59 and conformations 188 Morita-Baylis-Hillman alkylation and radical cyclization 974 and thermochemical data 206 1151 and SN1 reactions 456 strain energy 207 morphine, and resolution 167 and strain 208 molecular mechanisms, and Mosher’s acid, and absolute and symmetry 35 torsion strain 204 configuration 153 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2044 SUBJECT INDEX

Mosher’s ester, and absolute nanoparticles, and reduction of as a source of bromine 864 configuration 153 nitro compounds 1559 formation of haloamines 763 moving-bed chromatograph, and organometallics reagents, with halogenation of ketones 704 flow reactors 337 imines 1164 radical halogenation 862 MS, of carbocations 225 oxidation of alcohols 1458 with boranes 740 MTPA see Mosher’s acid nanosecond time-resolved Raman with DBU, and carbamates Mukaiyama aldol reaction 1180 spectroscopy 677 1371 and enol silyl ethers 1181 nanowires, Pt, reductive amination with HBr 864 and Nazarov intermediate 1181 1120 with sulfoxides 709 and silyl enol ethers 1181 naphthalene, alternant with vinyl carboxylic acids 887 enantioselective 1182 hydrocarbon 68 NCS (N-chlorosuccinimide), and environmentally friendly 1181 and aromaticity 61 allylic chlorination 863 homologous 1181 and complex formation 122 and ketones 707 Lewis base catalyzed 1181 and Dewar structures 59 and the Pummerer metal catalysts 1181 and MO calculations 59 rearrangement 1603 metal catalyzed 1182 and partial bond fixation 59 formation of haloamines 763 vinylogous 1181 and resonance 34 halogenation of ketones 704 Mukaiyama reaction see arenium ions 623 with boranes 740 Mukaiyama aldol reaction bond order 59 near-IR luminescence, and Mukaiyama reagent 1304 canonical forms 59 hydroamination, and lactones 1230 oxidation to naphthoquinones cyclization 926 formation of azides 532 1489 Neber rearrangement 1369 with ammonium thiocyanate oxidation to phthalic anhydride and azirene intermediates 294 and alcohols 533 1472 and azirenes 1369 Mulliken charges, and aromaticity resonance energy 60 and intermediate isolation 294 56 SEAr reactions 623 mechanism 1369 multicenter bonding 111 naphthoquinones, by oxidation of organocatalysts 1369 multiple bonds see bonds naphthalenes 1489 necklaces, molecular 128 +M and –M effects 376 naphthoxide, alkylation 481 Nef reaction 1098 and field effects 376 National Institute of Advanced aci form of nitro compounds myoglobin, engineered, with Industrial Science and 1099 diazoesters 1204 Technology see AIST alkyne anion with ketones 1144 myrtanylborane 935 Natural Products Updates 1625 mechanism 1099 Nazarov cyclization 742, 958 negative enhancement, and NMR N-alkylation, with enamines 587 and torquoselectivty 958 253 N-containing radicals 258 asymmetric 958 negative hyperconjugation 96, N-haloamides see amides decarboxylative 958 201 N-heterocyclic alkenes, phase interrupted 958 Negishi coupling 561 transfer catalysts 475 metal catalyzed 958 neighboring groups 424 N-heterocyclic carbenes see NHC retro- 958 alkenes and alkynes 427 N-iodosuccinimide, aromatic stereoselective 958 and cyclization 425 iodination 646 vinylogous 958 and electron density 428 N-methylmorpholine-N-oxide see with allenes 959 and first order rates 422 NMO Nazarov intermediate, and and halonium ions 425 N-methylpyrrolidinone see NMP Mukaiyama aldol reaction and NMR 429 N-nitroaniline see anilines 1181 and nucleophiles 428 N-nitroaniline, rearrangement 677 Nazarov-Wagner-Meerwein and phenonium ions 431 N-nitroso compounds 634 sequence 958 and rate 431 N-nitroso groups, rearrangement NBS (N-bromosuccinimide), and and rate enhancement 432 678 AIBN, ammonia, and and retention 427 N-oxides, and spin traps 252 aldehydes 872 and SN2 reactions 422 N, O-bis(trimethylsilyl)acetamide NBS, and aromatic halogenation and solvolysis 425, 428, 430, (BSA) see BSA 645 432 n→π* interaction 113 and formation of alkyl halides and the Heck reaction 812 NaBH4 see sodium borohydride from carboxylic acids aromatic rings 430, 432 NaCl see sodium chloride 1238 β- to leaving group 422 Nafion-H 642 and halogenation of carboxylic β-aryl 433 and hydration of alkynes 914 acids 708 C–C single bonds 433 nahuoic acid Ci(Bii) 1438 and radicals 862 C=C 427 named reactions 398 and the Pummerer cyclobutyl 430 Nametkin rearrangement, and rearrangement 1603 cyclopropyl 429 Wagner-Meerwein and Wohl-Ziegler bromination deactivation 847 rearrangement 1352 863 hydrogen 439 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2045

mechanism see mechanisms oxy-Michael reaction 978 enantioselective formation mechanism 422 stability 275 1022 and anti-dihydroxylation structures 275 enthalpy 276 1007 nickel boride, and hydrogenation from azides 276 methyl 438 1513 hydrogen abstraction 277 and NMR 438 nickel carbonyl, and insertion 277, 714 and Raman 438 hydrocarboxylation 984 enantioselective 715 participation by π bonds 425 with alkyl halides 604 mechanism 715 participation by σ bonds 425 with organometallics 743 metal catalyzed 715 participation, and nonclassical nickel catalyst 308–309 urea catalyst 715 carbocations 426 and cross coupling 561 reactivity 715 participation, and rate 422 and Ullmann reaction 798 rearrangements 277 principle of increasing electron nickel complexes, π-allyl 563 selectivity 715 demand 425 nickel peroxide 873 singlet 276 See also singlet propargyl groups 453 nickel-nanoparticles, and alkyl stereoselectivity 1023 σ-bonds 433 halide homocoupling trapping in a matrix 276 silyalkyl 439 559 triplet see triplet structural features 424 nickel, and Negishi coupling 561 triplet 276 neopentyl carbon, substitution catalyst with Grignard reagents with aromatic compounds 689 570 1024 neopentyl systems, and SN2 nickel, Raney see Raney nickel nitrenium ions 278, 837, 1369 reactions 450 nickel, Raney, hydrogenation of singlet and triplet 278 neopentyl tosylates, carbocation thiols and thioethers 883 nitric acid, AIBN, and conjugated formation 439 Nicotiana tabacum 1530 acids 874 neopentylithium 245 nitrate esters, and aromatic and nitration of aromatic neophyl radicals 1346 compounds 631 compounds 630 neutral radicals 855 nitrate, sodium, with and sulfuric acid 632 neutron diffraction, and hydrogen aryldiazonium salts 829 nitrosation of amines 761 bonding 108, 113 nitration of aromatic compounds, Raman spectra 632 Newman projections, and in ionic liquids 631 with alkanes, and radicals 711 conformations 189 nitration, acetanilide 632 with vinyl carboxylic acids 874 definition 189 aniline 632 nitric oxide, radical inhibitor 844 NHC (N-heterocyclic carbene) nitration, aromatic compounds nitrilases, hydrolysis of nitriles catalyzed, and boranes 630 1100 1554 and ionic liquids 632 nitrile hydratases, hydrolysis of conjugate addition 967 green procedures 631 nitriles 1100 NHC catalyzed, and cleavage of kinetics 632 nitrile imines, [3+2]-cycloaddition carbohydrates 981 rate of reaction 632 1246 and coupling of Grignard nitration, arylboronic acids 631 nitrile oxides, [3+2]-cycloaddition, reagents 881 of alkanes 711 in supercritical CO2 1032 and enantioselective reactions of aromatic compounds, radical dyotropic rearrangement to 275 pair formation 632 isocyanates 1437 and flow chemistry 275 of benzene, and intermediates ene reaction 953 and Heck reaction 275 294 from nitriles 1586 and ketones with aryl halides of N-nitroanilines 677 nitrile ylids, [3+2]-cycloaddition 819 of phenol 631 1029 and nitration of alkanes 711 ortho selective 631 nitriles, acid catalyzed addition of and tautomerism 101 with nitrate esters 631 alcohols 1257 and transesterification 275 nitrenes 223, 276–278, 1022, reaction with alcohols 1106 and vinyl boronates 936 1369 nitriles, acylation reactions 672 as metal stabilizing ligands 275 ab initio calculations 276 addition of amines 1126 basicity 275 acyl 1336 of ammonia 1126 catalyst 949 addition to alkenes 277 nitriles, alcoholysis 1106 Staudinger reaction 1058 and electric discharge 277 alkenes and acylium ions 1026 chiral 949 and photolysis 276 alkyl, with alkenes 831 definition 274 and rearrangements 1336 alkylation 579 Diels-Alder reaction 1037 aryl 276 amino 1212 for oxidation of aldehydes to by elimination of and hydrazoic acid 1117 carboxylic acids 1496 O-sulfonylamines 276 and Stephen reduction 1558 hydroacylation of carbonyl see carbonyl nitrenes and the Blaise reaction 1153 cyclopropanes 980 carbonyl 715 and the Hoesch reaction 672 nucleophilicity 275 definition 276 and the Pinner synthesis 1106 organocatalysts 275 dimerization 277 and the Ritter reaction 1257 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2046 SUBJECT INDEX

nitriles, alcoholysis (Continued) from alkyl halides 599 to aldehydes, reagents 1558 and the Thorpe reaction 1466 from amides 1327, 1460 to amines, and photochemistry and trimethylsilyl amides 1118 and the von Braun reaction 1557 nitriles, aryl from arylboronic 1327 and transfer hydrogenation acids 795 by the von Braun reaction 1557 and the Rosenmund-von Braun 1327 polymethylhydrosiloxane reaction 793 from amines 1460 1582 by photolysis of aryl ethers 794 from aromatic compounds 672 reagents 1556 formation, and metal catalyst from azides 1503 to hydrocarbons 1583 673 from carboxylate anion and to methyl with terpenes 1566 from aryl diazonium salts 828 cyanogen bromide 1260 to nitrile oxides 1586 from aryl halides 793 from carboxylic acids 601 nitriles, via Peterson alkenylation and DMF 794 and flow reactions 601 1192 from esters 673 from cyanide ion 599 vinylidene, hydration and from metal catalysts and from esters 601 cleavage 913 microwaves 7941 from hydrazonium salts 1325 with alkynes, from organometallics 673 from hydrosilanes 1584 cyclotrimerization 1078 from radical reactions 673 from hydroxylamine 1117 with amines 1492 preparation with metal catalysts from imines 1461 with boronic acids, metal 794 from iminium salts 672 catalysts 1169 nitriles, by addition of HCN to from ketones 1213 with Grignard reagents 1168 alkenes 991 from ketoximes 1326 flow reactions 1168 by an SN2 reaction 599 from nitro compounds 1564 with HCl and alcohols 1106 by dehydration of amides, and from oximes 1325, 1461 with hydrosilanes 1584 microwaves 1327 and acids 1326 with metals in ammonia 760 of amides, and Swern and fragmentation 1326 with organolithium reagents oxidation 1327 and rearrangement 1326 527, 1168 reagents for 1327 and the Burgess reagent with organozinc reagents, Blaise of oximes, and microwaves 1325 reaction 1169 1325 mechanism 1326 with trifluoroborates 1169 by dehydrogenation of amines solvent free 1325 nitrilium ions, and formation of 1460 from reactions with amides 1377 of amines, reagents for 1460 XtalFluor-E 1461 and the Schmidt reaction 1374 by fragmentation of oximes from silyl enol ethers 601 nitrite esters, from alcohols 504 1326 nitriles, halo, with boranes 593 nitrite ion, ambident nucleophiles by oxidation of amines 1460 heteroaryl, from heteroaryl 480 green catalysts 1460 halides 795 nitrite salts, with aryl halides ionic liquids 1460 hydrogenolysis 1584 874 by oxidation of hydrazones hydrolysis 600, 1099 nitrite, sodium see sodium 1462 to amides 1100 with alkenes 1315 by reduction of dinitriles 1584 to thioamides 1100 with HCl 761 by reduction of nitro and microwaves 1100 nitrites 1002 compounds 1563 hydroxy 585 nitrites, alkyl 710 by transfer hydrogenation 1582 indole, formation 673 from amines 504, 761 carbanions 240 Knoevenagel reaction 1188 with alkyl halides 530 catalytic hydrogenation 1557 metal catalyzed, addition of and metal catalyst 1024 condensation with nitriles 1209 amines 1126 nitro aldol reaction, conversion to ketones 1475 addition of alkenes 1258 enantioselectivity 1186 decyanation 760, 1583–1584 photochemistry 1584 nitro compounds, aci form 102, nitriles, dehydration of amides pKa 364 1099 1327 pKa, α-proton 579 and the Nef reaction 1099 of amides, and the Burgess radioactive 295 nitro compounds, and reagent 1327 reaction with carbocations tautomerism 102 of oximes, metal catalysts 1325 1257 and the Nef reaction 1098 reagents for 1325 reagents for hydrolysis 1100 and ultrasound 1559 nitriles, enzymatic hydrolysis reducing agents 1558 anion formation 480 1100 nitriles, reduction, hydride nitro compounds, aromatic, and formation of aryl ketones 672 reagents 1556 the von Richter nitriles, from alcohols 600 hydride reagents, metal rearrangement 834 from aldehydes 601, 1117, catalysts 1556 conversion to aryl carboxylic 1497 hydrogenation, metal catalysts acids 834 and hydroxylamine 1117 1556 electrochemistry and reduction reagents for 1118 to aldehydes 1557 1600 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2047

reduction, to anilines, reagents with alkyl halides 480 nitronium salts, nitration of 1560 with imines, enantioselectivity amines 761 to azobenzenes 1560 1166 nitronium tetrafluoroborate 631 to azoxybenzenes 1560 with sodium telluride 1600 nitroreductase BaNTR1 1564 to hydrazobenzenes 1560 base induced elimination 1329 nitrosamines, loss of HNO 762 to hydroxylamines 1560 nitro forms 102 nitrosation 634, 710 with dicarborane 1600 nitro groups, rearrangement 677 and enols 711 replacement of nitro with alkyl nitro-alcohols, by the Henry and UV 711 834 reaction 1185 aniline derivatives 635 with cyanide 834 from epoxides 523 of amides 761 with halocarbanions 820 nitro-Hunsdiecker reaction 874 of amines 761 nitro compounds, by oxidation, of nitroalkenes 1002 mechanism 761 isocyanates, with Michael acceptors 959 of ketones, mechanism 710 dioxirane 1503 nitrobenzene, and dipole moment phenol derivatives 635 of amines, reagents 1503 20 photochemistry 711 of hydroxylamines, reagents and Friedel-Crafts reactions nitroso aldol reactions 1180 1503 648 nitroso amides, base induced of nitroso compounds 1503 and M effects 376 elimination 1329 nitro compounds, canonical forms dipole moment 19 rearrangement 833 102 nitrogen containing Grignard nitroso carbamates, base induced cyanation 724 reagents 747 elimination 1329 from alkyl halides 530 nitrogen electrophiles 709 nitroso compounds 590, 1002, from aryl halides 874 nitrogen insertion 713 1502 from isocyanates 1503 nitrogen nucleophiles 512 nitroso compounds, and Barton from oximes 1503 nitrogen ylids 53, 835, 1202, 1382 reaction 1434 Henry reaction 1185 nitrogen ylids see ylids and formation of imines 711 hydrolysis 1098 nitrogen-to-oxygen rearrangement and tautomerism 102 hydrolysis, reagents for 1099 1330 and the Barton reaction 1434 oxidation to aldehydes or nitrogen, and molecular orbitals aromatic 634 ketones 1492 14 aryl and the Mills reaction 829 photochemical rearrangement and VSEPR 13 Fischer-Hepp rearrangement 328 as a leaving group 1310, 1330, 678 photochemistry 1563 1462, 1578 N-nitroaniline reagents for reduction 1563 bond angles 7 rearrangements 678 reagents, for hydrolysis 1099 cleavable groups 677 with anilines 829 nitro compounds, reduction 1563 electron structure 13 by oxidation of anilines 1502 to amines 1558 extrusion 1022 of anilines with Caro’s acid, hydrosilation 1561 from pyrazoles 1330 mechanism 1502 photochemistry 1561 from pyrazolines 1330 of hydroxylamines 1462 reagents 1558, 1560 from triazolines 1330 from amides 761 reductive alkylation 1561 leaving group 466 from amines 761, 1503 transfer hydrogenation 1560 PES spectrum 13 from nitro compounds 328 to azo compounds, reagents nitromethanes 116 from nitrous acids 710 1600 pKa 240 metal reduction to amines to azoxy compounds, reagents nitrones, azulenyl, and radicals 1561 1600 252 N-derivative, amines 590 to hydrazo compounds 1600 by oxidation, of amines 1462 N- versus C- 634 to hydrocarbons 1585 [3+2]-cycloaddition 1030 oxidation 1503 to hydroxylamines, reagents from amines 1504 oxidation to nitro compounds 1561 from hydroxylamines 1462, 1503 to oximes, reagents 1563 1503 preparation of diazomethane with Baker’s yeast 1560 from oximes 505 1329 with hydride reagents 1559 preparation and ball milling reduction to amines 1565 with metals, in acid 1559 1504 with oximes 762 mechanism 1559 with cyclopropanes 1033 nitroso ene reactions 953 with sodium telluride 1585 with Grignard reagents 1167 nitroso ureas, base induced and microwaves 1560 nitronic acids 102 elimination 1329 enantioselectivity 1559 nitronic esters, O-alkylation 480 nitroso-C compounds 635 on alumina 1560 nitronium ion 632 nitroso-halogenation, of alkenes nitro compounds, vinyl 874 electrophilic aromatic 1001 vinyl, by decarboxylation of substitution 633 nitroso-oxime tautomerism see radicals 874 migration from nitrogen 677 tautomerism with aldehydes or ketones 1185 preparation 632 nitroso-oximes 102 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2048 SUBJECT INDEX

nitroso, Diels-Alder reaction and antiaromaticity 74, 87 and methane 12 1053, 1055 and aromaticity 58 and methyl neighboring groups N-nitroso, isomerization to and arynes 774 438 C-nitroso 634 and benzene 55 and Mosher’s acid 153 nitrosoamines, from amines 761 and benzenonium ion 611 nonclassical carbocations 427, nitrosobenzoic acids, photolysis and Birch reduction 1525–1526 429, 435 328 and bond order 60 and norbornadienyl nitrosomethane, and tautomerism and bullvalene 1412 carbocations 427 102 and carbocations 225, and norbornyl carbocation 436 nitrosonium ion 634, 678, 711, 233–234, 429, 432 NMR, and organocuprates 555 823 stability 1337 and organometallics 245 nitrosyl chloride, with alkenes and chemical shift 19 and oxocarbenium ions 1381 1001 and chiral compounds 173 and paramagnetic ring current nitrosyl halides, with alkenes and chiral lactams 154 56 1001 and chiral shift reagents 174 and paratropic compounds 57, nitrosyl tetrafluoroborate 761 and chiral solvents 174 87 nitrotoluene, dipole moment 20 and CIDNP 253 and phenonium ions 432 nitrous acid, and amines 466 and conformation of and radicals 252, 254 and aniline derivatives 634 macrocycles 203 and ring current 55 and carbocation formation from and conformations 188 and rotaxanes 130 amines 235 and Cope rearrangement 1412 and solvolysis of esters 412 and diazotization of anilines and coupling constants 19 and spin traps 253 823 and crown ethers guest–host and steric strain 206 from alcohols 504 interactions 121 and tetramethylsilane 19 reaction with iminium salts 761 and cycloheptatrienyl anion and the Chichibabin reaction with amines 235, 761, 824, derivatives 77 823 1357 and cyclooctatetraene 76 and valence tautomerism 1414 mechanism 825 and cyclopropylmethyl anisotropy, and conformations with aromatic compounds 638 carbocations 438 188 with aziridines 1318 and cyclopropylmethyl cation annulenes 84, 87 with hydrazides 1371 437 calixresorcarenes 55 with hydrazines 761 and determining absolute chiral solvating agents 175 with hydroxy–amines 1357 configuration 153 cyclobutadiene derivatives 74 with nucleophiles 825 NMR, and diamagnetic ring NMR, database, chiral molecules nitrous oxide, [3+2]-cycloaddition current 55 155 1029 and diastereotopic compounds dynamic 203 nitroxide, and TEMPO 256 185 EtI + EtLi 253 radicals 256, 261 and diatropic 55 heptalene 67 asymmetric 259 and dynamic nuclear iodoethane and ethyllithium oxidation of alcohols 1452 polarization 254 254 nitroxyl radicals 256, 1463 and electronegativity 19 lanthanide shift reagents 153 and Bobbitt’s reagent 1453 and emission 253 Michael addition, TEMPO 256 and enantiomeric excess 173 organometallics 964–965 X-ray 257 and enantiomeric purity 175 negative enhancement 253 nitryl chloride, addition to alkenes and enol content 99 of carbocations, table 234 or alkynes 1001 and Fischer indole synthesis oxaphosphetanes 1197 with alkenes 1002 1420 paracyclophanes 50, 55 NMO (N-morpholine-N-oxide) and Friedel-Crafts alkylation rapid injection 555 1006 651 thio-Wittig reaction, and and dihydroxylation of alkenes and Grignard reagents 246–247 betaine 1197 1006 and homoaromatic compounds tri-tert-butylcyclobutadiene NMP (N-methylpyrrolidinone), 90 1414 solvent 1117 and hydroboration 933 tropone and tropolone 65 and nitrile formation 1117 and hydrogen bonding node 4 NMR (nuclear magnetic resonance 108–109, 111 and electron density 5 spectroscopy) 1621 and intermediates 294 NOESY, and π–π interactions 113 analysis, and stereochemistry and isotope effects 305 nomenclature, acid and base, 155–156 and isotopic labeling 295 IUPAC 339 and absolute configuration 153, and kekulene 84 ae and ea and conformations 155 and keto-enol tautomerism 99 197 and ABX pattern 155–156 and kinetics 302, 412 and Cahn-Ingold-Prelog system and alkenes 56 and mechanism 302 177 and annulenes 78, 81, 86 and Meisenheimer salts 769 and diastereomers 160 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2049

and IUPAC 224 norborandienone, metal complex nucleophiles 457 carbocations 224 116 nucleophiles, active methylene cis/trans, and dienes 177 irontricarbonyl complex 116 compound 566 D/L, and stereogenic atoms 148 norbornane, and twist acyl addition 1087 dig 288 conformation 195 addition to alkenes 895 E/Z 176 norbornene, and strain 217 nucleophiles, ambident 478 and alkenes 177 with thiols 1347 and basicity 480 and azo compounds 177 norborneol 181 and counterions 481 dienes 177 norbornyl bridgeheads, and and crown ethers 481 and imines 177 carbocations 413 and Kornblum’s rule 481 and thiocarbonyls 177 norbornyl carbocations 1352 and phenoxide ions 480 epi 159 ab initio calculations 436 and regioselectivity 478 erythro/threo 160 and NMR 436 and steric effects 481 g transitions 316 classical arguments 434 and thermodynamic control [i, i], and sigmatropic in stable solutions 435 480 rearrangement 1400 stability 435 cyanide 480, 600 peri- 159 norbornyl cation rearrangement, dianions 479 “r” and “s” 159 σ-participation 1352 enolate anions 479 R/S, and stereogenic atoms norbornyl compounds, and SN1 nitrite ion 480 149–152 reactions 414 nitro compounds 480 re/si 186 norbornyl sulfonates 455 solvent effects 481 syn/anti 161 norbornyl systems, and types 478 tet 288 nonclassical carbocations nucleophiles, and catalysis of trig 288 426 attack at carbonyls 1092 u transitions 316 and solvolysis 433 and cation affinity 459 nonaflates 466 norcamphor 181 and Lewis bases 459 non-alternant hydrocarbons 68 norcaradienes 1390 and neighboring groups 428 topological polarization 70 photochemical ring opening and nucleophilic aromatic non-concerted mechanism, and 1389 substitution 779 benzidine rearrangement norephedrine, benzoyl, and and nucleophilicity table 462 1424 rearrangement 379 and rate of reaction 461 nonconcerted, Cope normal acid, definition 350 and SN1 reactions 414, 459 rearrangement 1411 normal, Diels-Alder reaction and substitutions 403 nonadjacent π-bonds, stabilization 1050 and the periodic table 459 of carbanions 242 Normant reagents, addition to nucleophiles, approach to nonaflates, leaving groups 465 alkynes 951 carbonyl 1092 nonaflyl fluoride, with alcohols Norrish Type 1 cleavage, attack at ipso carbon 768 539 definition 326 carbon 545 nonalternant hydrocarbons, Norrish type I reaction, photolysis carboxylic acids 1218 calculations 69 of cyclobutanones 1331 catalysts for acyl addition nonaromatic rings, and arynes and radicals 1331 1092 774 Norrish Type II cleavage 327 charged, and solvent effects nonaromatic systems, and and elimination 1273 470 Huckel’s¨ rule 71 nortricyclane, and nonclassical counterions 481 nonbonded interactions 207 carbocations 435 definition 280 nonbonding orbitals 42 nortricyclyl chloride 274 dicarbonyl anions 479 carbocation 42 nosylates 465 directionality of approach to nonclassical carbocations 234, leaving groups 465 carbonyls 1092 425 See also carbocations notes, as a publication 1608 enolate anions 479 and neighboring group novel process windows 337 for aminosulfenylation 1025 participation 426 Nozaki-Hiyama reaction, heteroatom, conjugate addition and superacids 435 organochromium reagents 975 and temperature 435 1141 in SN2 reactions 459 stable solutions 435 with aldehydes or ketones 1141 nitrogen 512 nonclassical hydrogen bonds 107 nuclear magnetic resonance see on the arenium ion 633 nonconcertedness 678 NMR rate of reaction with nonhomoaromatic compounds 91 Nuclear Overhauser effect carbocations 459 nonionic bases 1233 spectroscopy see NOESY reaction with carbocations 236 nonplanar radical cations 266 nucleofugal ability, E1cB reaction with epoxides 497 nonplanarity, and aromaticity 80 mechanism 1284 reactivity order in nucleophilic nonpolar solvents see solvents nucleofuge 404 aromatic substitution 779 nonsynchronous, mechanism, and SNi reactions 443 strength of 459 [3+2]-cycloaddition 1031 nucleons 135 sulfur 506 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2050 SUBJECT INDEX

nucleophiles, approach to carbonyl reaction at carbonyls 463 and Meerwein-Ponndorf-Verley (Continued) π-nucleophilicity 892 reduction 1450 trajectory of approach to scale 464 flow reactions 1450 carbonyls 1092 solvent, scale 472 mechanism 1450 uncharged 460 nucleus-independent chemical metal catalyzed 1450 1,2 versus 14 addition 895 shift (NICS) 57 of alcohols 1450 with aziridines 575 Numerical Data and Functional supercritical conditions 1450 with conjugated carbonyl 895 Relationships in Science optical activity 133 with Lewis bases 575 and Technology 1620 and allenes 144 with nitrous acid 825 and biaryls 141 with π-allyl O-acylation, and enolate anions and biphenyls 141 palladium-complexes 564 1252 and chiral atoms 137 nucleophilic acyl substitution 670 with acyl halides 1252 and chirality 133 nucleophilic addition 281 O-acylhydroxamic acids see and circularly polarized light to alkenes 895 hydroxamic acids 157 to alkynes 896 O-alkylation 481 and light 156 nucleophilic assistance, and and amide formation 528 and paracyclophanes 145 solvents 472 and enolate anions 576 and polarizability 138 nucleophilic catalysis, hydrolysis enolate anions 479 and refractive index 156 of anhydrides 1218 nitronic esters 480 and restricted rotation 145 hydrolysis of anhydrides 1218 phenoxide ions 480 and solvolysis 433 nucleophilic mechanism 895, o-nitroanilinium ion, indicator for and symmetry 157 900, 1353 pK 352 cause of 156 and simple alkenes 899 O-sulfonylamines, elimination to determining absolute nucleophilic radicals 853, 902 nitrenes 276 configuration 153 nucleophilic reactions 280 O-tosyl imines, and the Neber meso compounds 137 nucleophilic rearrangement 282 rearrangement 1369 N, P, As, Sb 140 mechanism 1336 [1,3]-O→C rearrangement, perpendicular dissymmetric nucleophilic strength see metal-catalyzed 1405 planes 141 nucleophilicity orbital symmetry, optical antipodes 134 nucleophilic strength 459 [2+2]-cycloaddition optical inactivity 133 amides 527 reactions 1064 optical purity 173 and electron repulsion 463 observed rotation see optical resolution see resolution and functional groups 464 enantiomers, chiral optical rotatory dispersion 154 table 462 compounds and conformations 188 substitution see substitution α, definition 135 optically active, boranes 1146 with hetero multiple bonds octahydro[14]annulene 82 homogeneous hydrogenation 1087 octahydroannulene 82 catalysts 1529 nucleophilicity 410 octahydroindolizine 1433 organogold reagent 549 ambident nucleophiles 480 octatetraenes, cyclization to orbital interaction, and bond and basicity 459 cyclooctatrienes 1396 strength 31 and Brønsted-plots 463 octylidenes 269 orbital lobes, overlap 1393 and polarizability 480 odd alternant hydrocarbons see orbital movement, and rate of reaction 461 alternant hydrocarbons [1,5]-sigmatropic and solvation 460 odorless, thio-Michael addition migration of carbon 1405 and solvents 460, 470 978 orbital overlap 1046–1047 and steric hindrance 461 oxetenes, from Paterno-Buchi¨ and ring closing of dienes and supercritical carbon dioxide reaction 1060 1392 474 Official Gazette of the Patent [4+2]-cycloaddition 1051 and Swain-Scott equation 461 Office 1613 cyclopropane 209 and the α-effect 463 olefins see alkenes ketenes with cyclopentadiene and the Periodic table 459 olefin metathesis see metathesis, 1065 and unshared electrons 463 alkene [1,3]-sigmatropic at carbonyl carbon 463 olefination see alkenylation rearrangement 1401 in nucleophilic aromatic olefination, Peterson see Peterson orbital symmetry, and substitution 779 oligocatenanes 128 cyclobutene-butadiene in SRN1 reaction 779 oligorotaxanes, cyclic 128 1396 of nucleophiles, table 462 onium salts, from amines 358 and Mobius-H¨ uckel¨ method of the tetrafluoroborate anion with alcohols 498 1396 829 online literature searching 1633 and stereochemistry of order, for SN2 reactions 462 problems 1633 electrocyclic order, toward sulfonyl sulfur Oppenauer oxidation 1450 rearrangements 1396 1267 and alkoxide bases 1450 conservation 1358 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2051

cyclopropane ring opening overlap 92 aza-Michael reaction 976 1397 1s-orbitals 4 aziridination of alkenes 1024 principle of conservation 1045, orbitals, sp 8 Baeyer-Villiger reaction 1379 1063 orbitals, sp2 hybrid 9 Baylis-Hillman reaction 1150 rules 1045 orbitals, sp3 15 Cope rearrangement 1409 and stability of Dewar hybrid 9 [2+2]-cycloaddition 1059 benzenes 1396 orbitals, ungerade 6 cyclopropanation 1072 orbitals 4 ORD see optical rotatory Diels-Alder reaction 1037 allylic carbocations 42 dispersion intramolecular 1042 alternant and non-alternant Organic Chemistry: An Acid–Base dihydroxylation 1007 hydrocarbons 69 Approach 1627 enolate anions 584 and allenes 144 organic compounds, and bond for epoxidation 1013 and benzene 35, 38 energy 32 halogenation of epoxides 541 and bond angle 27 Organic Electronic Spectral Data halogenation of ketones 705 and bond distance 26 1622 halolactonization 999 and conjugation 42 Organic Functional Group Henry reaction 1186 and cyclopropane 209 Preparations 1630 hydrosilation 941 and delocalization 33 Organic Reaction Mechanisms hydroxylation of alkyl 1477 and ethyne 11 1623 ketones, with HCN 1210 and ferrocene 66 Organic Syntheses 400, 1628 Mannich reactions 1124 and hybridization 8 Collective Volumes 1628 Michael reaction 960 and hyperconjugation 94 Indexes 1628 N-heterocyclic carbenes 275 and metallocenes 66 Reaction Guide 1629 oxy-Michael reaction 977–978 and mutual repulsion 8 Organic Synthesis, 4th edition Pictet-Spengler reaction 655 and photoelectron spectroscopy 1627 reductive amination 1121 (PES) 13–14 organization, Beilstein, table 1618 Robinson annulation reaction and rearrangement 1335 Organization, Chemical Abstracts 1179 and resonance 34 1615 Strecker synthesis 1211 and thermal ring opening of organoaluminium compounds, sulfur ylids, and cyclobutenes 1392 with aldehydes or ketones cyclopropanation 1207 and trienes 44 1139 thio-Michael addition 978 and ylids 52 organoaluminum reagents 559 transesterification 1233 orbitals, antibonding 5, 10 organobismuth reagents 549 transfer hydrogenation 1528 of butadiene 40 organoboranes see boranes Vitamin B2 1506 bonding 5, 10 organoboranes 735 organochromium compounds, d-orbitals 16 organoboranes, allylic addition to Nozaki-Hiyama reaction and carbanion stability 241 aldehydes or ketones 1145 1141 overlap, carbanions 693 to aldehydes or ketones, with aldehydes or ketones, diagrams 4 enantioselective 1145 enantioselectivity 1141 dienes-cyclobutene conversion to amines 741 organocopper reagents, and interconversion 1392 organoboronates, from Grignard diethylzinc 558 five-membered ring reagents and carbon and Lewis acids 555 heterocycles 62 dioxide, metal catalyzed conversion to cyanides 744 gerade 6 1161 organocopperzinc reagents, with hybrid 9 organoboronic acids, with sulfinate allyl halides 558 hybrid, 2p 8 salts 511 organocuprates, addition to linear combination of 6 organocalcium reagents, and alkynes 951 molecular see molecular radicals 248 aggregation states 961 orbitals and SET mechanism 248–249 and alkyl halides, mechanisms molecular 5, 34 organocatalysts 309–310, 584 555 nonbonding 42 aldol condensation 1177 and Cu(III) complexes 962 of mercury 8 amines to amine oxides, and cyclopropylcarbinyl halides of oxygen atom 7 oxidation 1504 444 and vinyl carbocations 448 and conjugate addition, borates and inversion of configuration conjugated with double or 968 558 triple bonds 42 and epoxides and anilines 523 and Michael addition 960 π-orbitals 10 and the Michael reaction and NMR 555 π∗-orbitals 10 955–956, 959 and racemization 558 alkenes 901 and the Neber rearrangement and retention of configuration p 10 1369 558 2p-orbitals 4 and the pinacol rearrangement and SN2′ reactions 444 σ-orbitals 5, 10 1354 and structure of alkyl halides shape 11 and the Ritter reaction 1258 556 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2052 SUBJECT INDEX

organocuprates, addition to and sparteine 551 with alkenes 947 alkynes (Continued) and the Barbier reaction 1134 with alkyl sulfates 552 conjugate addition 960 and the Shapiro reaction 1308 with alkyl sulfonates 552 cyano 962 and the Wurtz reaction 749 with alkynes 947 dummy ligands 962 and TMEDA 247–248 with allylic halides 552 excess reagent required 961 and Wittig rearrangement 590 with amides 1158 from organolithium reagents and Ziegler alkylation 806 with amines 1383 744, 961 aryl, hydrolysis 686 with aryl amines, halogen-metal exchange 557 unsolvated 247 rearrangement 1384 higher order 557 association 749 with aziridines 1034 organocuprates, higher order organolithium reactions, bases with boronic esters 595 mixed 556 350 with carboxylate salts 1154 and conjugate addition 961 cleavage of ethers 571 with carboxylic esters 1157 conjugate addition 979 complex with boron with carbon dioxide 743 structure controversy 557 compounds 964 with carbon monoxide 551 organocuprates, in water 962 configurational stability 243, with copper compounds 555 intermediates 556 750 with cyclic ethers 1301 limitations in conjugate conversion to amides 743 with cyclic sulfones 1332 addition 962 coupling 551 with dihalocyclopropanes 1359 to reactivity 556 with sulfones 567 with dithianes 588, 1438 mechanism of reaction 556 covalent C—Li bond 749 with epoxides 571 mixed 556 cryptands 1135 and sparteine 1135 and conjugate addition 961 cyclization 948 with ethers 1301, 1384 oxygen mediated coupling 882 dehydrohalogenation 1313 Wittig rearrangement 1384 preparation 745 deprotonation 733 with imines 1162 selectivity in transfer reactions EtI and NMR 253 chiral auxiliaries 1162 962 exchange with alkyl halides enantioselectivity 1164 SN2 reactions 556 237 with iron pentacarbonyl 821 SN2′ reactions 555–556 with alkyl halides 1134 with isocyanides 1265 solvent effects 961 formation in flow reactors 337 with isonitriles 1169 substrate compatibility 963 of organocuprates 744 with ketones 1129 thermal stability 555 organolithium reactions, from with metal catalysts 948 tolerated functional groups 962 alkyl halides 749 with methoxyamine 741 1,2- versus 1,4-additin 963 from alkyl halides 750 with nitriles 527, 1168 with acyl halides 1154 and lithium 1134 with oxazines 591 with aldehydes or ketones 1143 from organolithium reactions with phosphonium salts 1194 with alkenes 948 1129 with siloxanes 822 with alkyl halides 555 from thioethers 884 with silyl enol ethers 722 stereochemistry 558 gem-dihalides 1136 with sparteine 948 with enol acetates 563 halo 750 Wurtz coupling 750, 1132 with epoxides 572 in THF 247 X-ray structure 247–248, 749 with sulfonate esters 556 mechanism of formation 751, organomagnesium compounds with trialkylsilyl halides 961 1135 exchange with R2Hg 238 organogallium reagents 563 metal catalyzed conjugate and carbanions 238 organoindium reagents 562, 570 addition 979 by hydroboration 548 organolanthanide catalysts, Michael addition, conjugated organomagnesium reagents see hydroamination 1021 aldehydes 963 Grignard reagents organolithium reactions 165, 243, Michael reaction 1159 organomanganese compounds 245, 548 mixed aggregates 548, 1134 559 aggregates 750, 1134 organolithium reactions, with alkenes or allenes 948 aggregation state 247, 1162 precursors to organomercury compounds, alcohol coupling 569 organocuprates 961 exchange with R2Mg 238 and ate complex 751 preparation of organometallics leaving groups, and SE2 and carboxylic acids 1153 731 reactions 696 and CIDNP 751 + RI, radical intermediates 253 organometallic reagents 548 and deep eutectic solvent 1130 solvent effects 750 addition to aldehydes or and diastereoselectivity 1135 sonochemical preparation 333 ketones, metals and DME 247 sterochemistry 750 1136–1142 and electron affinity 247 structure 247 addition to alkenes 946, 948 and enantioselectivity 1135 1,2 versus 1,4 addition 1131 addition to alkynes 948 and flow reactions 548 Weinreb amides 1159 allyltin 1138 and radicals 751 intramolecular 1159 amination of 741 and solvation 247 with aldehydes 1129 and acid–base reactions 732 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2053

and acyl halides, formation of transmetalation 744, 746 with alkyl halides 559 ketones 670 vinyl, formation of divinyl with nitriles, Blaise reaction and carbanions 237 ketones 603 1169 and carbonylation of aryl Weinreb amides 1159 orientation, alkenes 1290 halides 822 organometallic reagents, Zaitsev 1290 and metalation 730 with acyl halides 1155 ortho effect 622 and NMR 245 with aldehydes or ketones 166, and rate of reaction 389 and oxygen 734 1136 ortho esters, hydrolysis 487 and peroxides 735 with alkene–aldehydes 1143 reduction to acetals 1574 and the Heck reaction 811 with alkenes 948 transetherification 496 and the Stetter reaction 1143 with alkyl halides 558–563, with diketones 1103 and the Ullman reaction 559 603 with Grignard reagents 570 organometallic reagents, aryl 685 mechanism 559 with hydride reagents 1574 hydrolysis 686 with alkyne–aldehydes 1143 ortho metalation, directed 552 with alkyl halides 805 with alkynes 948 ortho rearrangement, Claisen with aryl halides 795 with amides 1158 rearrangement 1415 organometallic reagents, bases with aryl halides 1143 ortho selective nitration 631 350 with aryldiazonium salts 830 ortho substitution 615–616 bimetallic compounds 951 with azetidines or aziridines rearrangement, steric effects bis addition to alkynes 951 574 1383 by decarboxylation 754 with carbon dioxide, ortho/para selectivity, and aryl carbonylation 603, 605, 742 enantioselectivity 1161 radicals 854 flow reactions 743 with carbon disulfide 1161 orthoesters, and transacetalization catalyzed coupling 882 with carboxylic esters 1157 1103 cleavage of ethers 571 with carboxylic esters and orthoformates 1104 conjugate addition 960, 963 thioesters 1158 with sulfonic acids 1268 diastereoselectivity 962 with conjugated carbonyl orthogonal conformations 195 mechanism 963 compounds 960 Orton rearrangement 679 conversion to amides 743 with conjugated esters 1143 and peroxides 679 conversion to amines 742 with epoxides 571–572 intramolecular 679 conversion to cyanides 743 with halogens 739 photochemical 679 conversion to esters 738 with imines, ionic liquids 1163 osazone test, and hydrazines 1116 coupling 567, 882 sonication 1164 osazones 1116 with alcohols 568 with methoxyamine 740 and sugars 1116 with carboxylic esters 563 with sulfonyl halides 1270 from α-hydroxy aldehydes and with vinyl triflates 717 with sulfuryl chloride 738 ketones 1116 deprotonation 733 organopalladium reagents 548 oscillation, carbanions 243 enantioselectivity 733 organosilanes see silanes osmapentalyne 89 dienes and carbon dioxide 988 organosodium compounds 554 osmate esters 1006 organometallic reagents, formation with ethers 1301 osmium catalysts 309 of aryl nitriles 673 organotin reagents 562 magnetically recoverable 1008 formation of arylamines 786 organotitanium compounds see osmium complex, and formation of diaryl ketones 723 Petasis reagent, Tebbe dihydroxylation 1006 from alkenes 937, 946 reagent osmium tetroxide, and chiral from alkyl halides 746, 750 organotitanium compounds, with additives 1008 from metal halides 744 aldehydes or ketones and dihydroxylation of alkenes from metals 746 1140 1005 from organolithium reagents with Grignard reagents 745 and Sharpless 731 with alcohols 569 aminohydroxylation 1019 from organometallics 730, organotrifluoroborates, catalysts, with Cinchona 744–745 preparation 737 alkaloids 1006 Keck allylation 1138 stability 737 encapsulated 1006 magnesium 548 UV and formation of radicals ionic polymer supported 1009 metalation 730 338 microencapsulated 1009 Michael addition 964–965, organozinc compounds 549 polymer bound 1006 1159 organozinc compounds, and toxicity 1006 enantioselective 964–965 carbenoids 1074 with alkenes 1006 other, with aldehydes or and the Reformatsky reaction with Jones reagent 1471 ketones 1139–1142 1152 with Oxone 1471 preparation 731 dimethylzinc 562 out–in isomers 181–182 See also preparation of ketones 603 formation of dienes 560 isomers structure 244–249 with aldehydes or ketones 1140 out–out isomers 182 sulfuration 738 with alkenes 949 overmethylation, and amines 514 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2054 SUBJECT INDEX

over oxidation, alcohols, oxidation oxazolidinone amides, conversion loss of hydrogen or gain of with Cr(VI) 1448 to methyl esters 1234 oxygen 1439 overall rate 299 oxazolines, alkylation 592 metal catalysts 1477–1478 overlap of orbitals, in HOMO conversion to carboxylic acids of acid sensitive compounds 1391 592 1448 overlap, of orbital lobes 1393 oxazolone, mechanism of oxidations, of alcohols 1447 Overman rearrangement 1418 Dakin-West reaction 756 and Burgess reagent 1451 oxa-di-π-methane rearrangement oxepin, and Cope rearrangement and Grubbs’ catalyst 1458 1433 1414 by catalytic dehydrogenation Oxa-Pictet-Spengler reaction 656 oxetanes, and formation of 1454 enantioselective 656 isonitriles 527 DMSO with various reagents oxacyclooctane, conformation and photochemical 1451 203 [2+2]-cycloaddition 1060 Fe/9-azabicyclo[3.3.1]nonan-N- oxaloacetic acid 184 by Paterno-Buchi¨ reaction oxyl 1452 oxalyl bromide, with carboxylic 1060 H2O2, flow reactions 1455 acids 1251 cleavage with organolithium reagents, utilized with DMSO oxalyl chloride, and DMSO, reagents 571 1451 oxidation of alcohols 1451 conformation 202 with alternative hypervalent with carboxylic acids 1251 desymmetrization 490 iodine reagents 1454 oxamic acid 102 from ketene acetals 1261 with Bobbitt’s reagent 1453 oxammonium salt, alcohols, hydrolysis 490 with chromium (VI) 1447 oxidation to carboxylic in the Prins reaction 1213 mechanism 1449 acids 1492 protonated 1213 with Dess-Martin Periodinane oxaphosphatanes 1196 vinyl, conversion to 1453 mechanism, Wittig reaction dihydropyrans 1408 with DMSO reagents 1451 1196 with (EtO)3SiCl 542 with H2O2 1455 NMR 1197 with amines 524 with hypervalent iodine 1453 stereochemistry 1197 oxidation number 1439 with metals 1455–1458 oxaspiroheptane 1416 oxidation number, functional with miscellaneous reagents oxathiazinane 713 groups, table 1440 1455–1458 oxathiolanones, extrusion to give oxidation reagents, and with nitroxyl radical 1452 alkenes 1332 Jacobsen-Katsuki with oxoammonium salt twofold extrusion 1332 epoxidation 1017 1453 oxatriquinene 235 dimethyl dioxirane 1455 with TEMPO, co-reagents oxazaborolidine catalyst 310 enzymatic 1455 1452 oxazaborolidines, chiral in for alcohols 1447 in ionic liquids 1452 reductions 1544 for ozonides 1466 solvent free 1452 oxazine carbanions with epoxides KMnO4 1006 with TPAP 1454 591 oxidation state, of functional oxidations, of aldehydes to oxazine-2-ones 1105 groups 1439 carboxylic acids 1495 from 1,3-isocyanates and oxidations 282, 1441 to carboxylic acids, mechanism oxetanes 1105 oxidations, agents, hypervalent 1495 oxazines 1053–1054 iodine 1454 N-heterocyclic carbene alkylation 591 oxidations, allylic see allylic catalysts 1496 from nitrones with oxidation to carboxylic acids, reagents for cyclopropanes 1033 oxidations, allylic, Sharpless 1495–1497 with Grignard reagents 591 method 1482 oxidations, of alkanes, with organolithium reagents with selenium dioxide 1481 Chloramine-T 1477 591 and DMSO 1490 nanocrystalline cobalt oxide oxaziridination 1208 boranes, mechanism 1385 1477 oxaziridines 139 Boyland-Sims 674 oxidations, of alkenes to aldehydes oxaziridinium salts 1015 cathecols and hydroquinones, or ketones, metal catalysts and epoxidation of alkenes and isotope labeling 1460 1499 1014 and radicals and radical ions to aldehydes or ketones, metal from Oxone and iminium salts 1460 catalysts 1499 1014 CH, aryl methyl, and radicals to ketones, reagents 1499 oxazolidin-2-ones, N-alkylation 1481 to allylic alcohols 1478 529 reagents for 1481 chromyl chloride 1478 1,2-oxazolidines 139 definition 1439 oxidations, of alkyl halides, and oxazolidines 139 diarylhydrazines, reagents for the Kornblum reaction from alkynes 987 1462 1490 from aziridines 765 hydrocarbons to amines 1487 and the Kornblum reaction, oxazolidone amides 1235 Lavoisier’s definition 1439 reagents 1490 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2055

to aldehydes 1490 of aromatic compounds, and the O-alkyl, from oximes 494 to aldehydes, Sommelet Dakin reaction 1473 oxidation 1503 reaction 1490 reagents 1472 to nitro compounds, reagents oxidations, of allylic alcohols of cyclic ketones to dicarboxylic 1503 1448 acids 1465 photoisomerization 328 metal catalyzed 1449 reagents for 1465 radical addition 1217 oxidations, of amines to amine of diamines 1464 reagents, for Beckmann oxides, enantioselectivity of diols 1463 rearrangement 1375 1504 by lead tetraacetate, cyclic oximes, reduction to aziridines mechanism 1504 transition state 1464 1563 organocatalysts 1504 mechanism 1464 to imines, enzymes 1564 reagents 1504 enantioselectivity reagents 1563 of amines, reagents for 1492 1463–1464 with Baker’s yeast 1562 with manganese dioxide mechanism 1464 with hydride reagents 1563 1462 with lead tetraacetate 1463 enantioselectivity 1563 of anilines to azo compounds with periodic acid 1463 reagents 1555 1462 of enol ethers 1472 oximes, stereoisomers 1115 of aromatic hydrocarbons, to of phenylenediamine 1472 with alkyl halides 505, 1217 quinones 1489 of silyl enol ethers 1509 with aryldiazonium salts 830 of aromatic side chains 1472 with dimethyl dioxirane 1464 with diazoalkane 494 mechanism 1473 with ozone see ozonolysis with Grignard reagents 1166 reactivity 1473 oxidative decarboxylation 1474 with nitroso compounds 762 reagents for 1473 oxides, amine see amine oxides with phosphorus pentachloride relative reactivity 1473 oxides, phosphine see phosphine 1375 structural limitations 1473 oxides oxindoles 529 of benzylic halides, and the oxime esters, conversion to fluorination 705 Krohnke¨ reaction 1491 amides 1377 oxiranes, antiaromatic 1015 of boranes, to alcohols 1385 conversion to diamines 1596 divinyl, Cope rearrangement of boronates 1387 electroreduction 1596 1410 of cathecols and hydroquinones, from alkyl halides 506 Friedel-Crafts alkylation 650 and autoxidation 1460 from oximes 506 vinyl 1368 with Fremy’s salt 1459 oximes, acid catalyzed formation with metal oxides 503 of diols 1006, 1457 of nitriles 1326 oxiranyllithium reagents, and oxidations, of hydrazones, to addition of HCN 1212 carbenoid insertion 730 nitriles 1462 alkylation 505 oxirene intermediate 1364 hydrocarbons 1476 and Beckmann rearrangement oxirenes 1015 Gif system 1477 1461 and Wolff rearrangement 1365 of α-ketones, reagents for 1487 and tautomerism 101 oxo analog, Povarov reaction of methyl groups, Barton aryl, Bamberger rearrangement 1054 reaction 1434 836 oxo gold carbenes 729 of phenols 1441, 1459 by reduction of nitro oxo process 989 reagents 1459 compounds, reagents 1563 oxoammonium salts, oxidation of of silanes, with hydroperoxide catalytic hydrogenation 1555 alcohols 1453 499 conversion to anilines 836 oxocarbenium ions 230, 235, of thioethers, ionic liquids to nitriles 1461 1089 1506 cyclic, and Beckman and aldol condensation 1178 mechanism 1506 rearrangement 1375 and NMR 1381 reagents for 1505–1508 dehydration 1325 and super acid 1381 Oppenauer see Oppenauer to nitriles 1325 and the Prins reaction 1214 oxidation and microwaves 1325 and transetherification 496 remote 1477 metal catalysts 1325 as catalysts 310 Swern see Swern reagents for 1325 formation 1359 Tamao-Fleming 499 with the Burgess reagent in the Prins reaction 1213 trimethylsilyl ethers 1458 1325 lifetime 235 oxidative amidation 873 oximes, E/Z isomers 1115, 1338 resonance stabilized 1089 oxidative cleavage, of alkenes esters, with acids 1377 oxocarboxylic acids 102 1467, 1470 fragmentation to nitriles 1326 tautomerism 103 Barbier-Wieland procedure from ketones 710 oxoglutaric acid 184 1471 from nitro compounds 1563 Oxone, and allenes 914 reagents for 1470, 1472 from nitronic esters 480 and haloamines 763 with Lemieux-von Rudloff from nitrous acid 710 and oxidation of hydrazones reagent 1470 from oximes 830 1462 of alkyl halides, with base 1508 hydrolysis 836, 1097 and oxidative amidation 873 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2056 SUBJECT INDEX

Oxone, and allenes (Continued) and α-hydroxylation of ketones intermediate, dioxirane 1470 and oxidative cleavage of 1484 hydroperoxides 1468–1469 alkenes and alkynes 1471 atom, and orbitals 7 mechanism 1467 cleavage of diketones 1465 cycloaddition to dienes 1055 of alkenes 1466 oxidation of alcohols 1458 diradicals 867 and rearrangement 1467 oxidation of amines to formation of cyanoamines 724 mechanism 1467 hydroxylamine 1502 insertion reactions 1365 of cyclic alkenes 1467 oxidation of cathecols and hydrocarbons, mechanism synthetic applications 1466 hydroquinones 1459 1477 oxidation of oximes to nitro reagents 1477 p character, and bond angle 28 compounds 1503 oxidation of trimethylsilyl and hyperconjugation 94 oxidation of trifluoroborates ethers 1459 P-P bonding 183 1387 radical inhibitor 844, 975 P, π-dihydrobenzooxaphosphole with iminium salts 1014 reactivity in autoxidation 867 ligands 312 with OsO4 1471 singlet see singlet oxygen Paal-Knorr furan synthesis 1114 oxonin 79 triplet see triplet oxygen Paal-Knorr pyrrole synthesis 1114 oxonium ions 424–465, 489 with benzene 780 flow reactions 1114 alkylating agents 498 with ethers 867 mechanism 1114 alkynes with alcohols 916 with Grignard reagents 734 Paal-Knorr reactions, in deep and dioxane 419 radical intermediates 734 eutectic solvents 1114 and hydration of alkenes 912 with hydrocarbons 867 Paal-Knorr thiophene synthesis and solvolysis 419 with organometallic reagents 1114 cleavage 540 734 palladacycle catalysts 813, 986 X-ray 235 oxymercuration–demercuration palladium acetate, acyloxylation of oxonium salts, from alkyl halides 913 alkenes 871 502 oxymercuration, and back palladium catalyst 311 from ethers 502–503 donation 913 alkyne cross coupling 597 oxy-Cope rearrangement 1409 and Markovnikov’s rule 913 and dehydrogenation of ketones antibody catalyzed 1410 and NaBH4 913 1446 flow reactions 1409 of alkenes 913 and Rosenmund reduction 1549 oxy-Michael reaction, and of alkynes 914 and Sakurai reactions 966 organocatalysts 977 of vinyl halides 483 and selenide formation 510 enantioselective 978 ozone 59 and Sonogashira coupling 308, intramolecular 977 and mechanochemistry 338 816 N-heterocyclic carbenes and oxidation of hydrocarbons and Stephens–Castro coupling catalysts 978 to alcohols 1476 816 organocatalysts 978 and oxidative cleavage see and Suzuki-Miyaura coupling oxyallyl cation, and ultrasound ozonolysis 799 333 and phenanthrene 60 and the Heck reaction 308, 811 oxyamination, and carbamates [3+2]-cycloaddition 1030 and the Stille reaction 560 1020 dipolar addition with alkenes and the Tsuji-Trost reaction enantioselectivity 1020 1467 308, 564 of alkenes 1019 formation of ozonides 1466 and the Wacker process 1499 oxychlorocarbenes 274 ozonides, from ozone and alkenes arylation of amines 787 [2,3]-oxygen-to-sulfur migrations 1466 arylation of ketones 819 1422 isolable 1469 arylation of silanes 822 oxygen-18, and labeling 486 oxidation of 1466 boronic acids with carboxylic oxygen, and autoxidation 867 reduction, reagents for 1466 acids 1154 and conjugate addition of stereochemistry of formation carbonylation of aryl halides boranes 967 1468–1469 821 and coupling of organocuprates ozonolysis 1466 complex, chiral 1379 882 alkenes versus alkynes 1467 complexes 44 and dehydrogenation of ketones and isotope labeling 1469 coupling of vinyl groups 560 1446 and alkene structure 1466 cyanation or aryl triflates 672 and electronic structure 16 and carbonyl oxides 1468 diacetoxylation 1009 and ene reactions 869 and gas phase 1470 fluorination of oxindoles 705 and heptalene 67 and ion pairs 1467 Heck reaction 811 and radical conjugate addition and radicals 1467 palladium-polymer supported, 969 and sterochemistry 1468–1469 catalyst 787 and the Glaser reaction 876 and trioxolanes 1467 pancreatic porcine lipase, and the Hay reaction 876 and zwitterions 1467 formation of lactams 1243 and α-hydroxylation of ketones Criegee mechanism 1467 peroxo complexes 802 1483 dipolar addition 1467 polyene cyclization 944 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2057

thiocarbamate formation 765 photosensitization 1061 pentalene derivatives 67 trifluoroborates with aldehydes transposed 1061 and aromaticity 67 1147 with quinones 1060 pentan-2,4-dione, enol 100 Wacker process, mechanism Pauli exclusion principle 4, 251, pentasila-1,4-diene 46 1500 316 pentasulfides 511 π-allyl complex 44, 1431 Pauli repulsion, and bond energy peptide catalysts, Michael π-allylic 564 32 reactions 959 para migration, and Fries Pauling scale of electronegativity peptide synthesis and Ugi reaction rearrangement 676 17 1265 para rearrangement, and the Pauson-Khand reaction, and peptides, via solid-supported Wallach rearrangement alkene carbonylation 985 synthesis 1244 1436 and flow reactions 986 perborate, sodium see sodium para selectivity, arylazo and microwaves 986 perbromides, with Chloramine-T compounds 679 and ultrasound 986 1003 para substitution 615–616 double 986 perchlorate, lithium, catalyst 661 para-Claisen rearrangement 1415 enantioselective 986 perchlorotriphenylamine 146 paracyclophanes 50 functional group compatibility perdeuteration, cyclic alkanes and chirality 145 986 698 and planarity 50 intramolecular 986 perepoxides 869 and resonance 49 mechanism 987 perhydrotriphenylene, as host 124 and restricted rotation 145 back donation 987 pericyclic, addition 281 and spectroscopy 50 metal catalyzed 987 mechanism 280, 869, 912 and strain 50 photochemical 986 and the Prins reaction 1214 and X-ray 50 pseudo 985 pyrolysis of homoallylic heterocyclic 50 silicon tethered 986 alcohols 1328 NMR 55 substrate compatibility 986 [3,3]-sigmatropic paraformaldehyde, and the with allenes 986 rearrangement 1415 Eschweiler-Clarke Payne epoxidation 1380 transition state, synchronous procedure 1121 Payne rearrangement 497 1037 from formaldehyde 1259 PCC (pyridinium chlorochromate), periodate, and oxidation of paraldehyde, and acetaldehyde oxidation of alcohols 1448 Cathecols and 1259 acidity of 1448 hydroquinones 1459 paramagnetic ring current 56–57 rearrangement of allylic periodic acid, and Lemieux-von and paratropic compounds 57 alcohols 1448 Rudloff reagent 1470 paratropic annulenes 86 PCl5, with malic acid 296 and oxidative cleavage of diols paratropic compounds 57, 87 PDC (pyridinium dichromate), 1463 antiaromaticity 87 oxidation of alcohols 1448 with diols, mechanism 1464 NMR 87 Pechmann condensation, and periodic readings, and kinetics paratropic, bridged annulenes 87 microwaves 654 300 dipleiadiene 87 formation of coumarins 654 periodic table, trends in Lewis pyracyclene 87 Friedel-Crafts cyclization 776 acidity 366 partial bond fixation 59 Montmorillonite K-10 654 and acidity 365 partial molar volume, and high PEDOT, and the pinacol coupling and bond energy 31–32 pressure 478 1594 and Lewis acids 358, 365 partial rate factors 619, 629 PEG [poly(ethylene) glycol] 391 and nucleophiles 459 aryl radicals 854 and nitrile hydrolysis 1100 and nucleophilicity 459 definition 625 and oxy-Michael 978 trends in Brønsted-Lowry σ-participation, norbornyl cation and rate enhancement 391 acidity 366 rearrangement 1352 and the Baylis-Hillman reaction periodinane, Dess-Martin 532 rearrangements 1352 1150 Perkin reaction 1189 partitioning effects, and SNAr polyethylene glycol 1150 permanganate potassium and reactions 770 PEG-400 510, 599, 665 oxidation of sulfoxides with arenium ions 609–610 pentacoordinate transition state 1505 Passerini reaction 1264 404 and Lemieux-von Rudloff mechanism 1265 pentacoordinated ions 224 reagent 1470 solvent free 1265 pentadienes, and geminal bond allylic alcohols 1450 Pasteur, Louis, and resolution 170 participation 1403 oxidation of alcohols 1450 Patent Office, Official Gazette pentadienyl radicals 255 permanganate, with alkenes 1006 1613 pentadienylium ion 225 with crown ethers 1470 patents 1609 pentaerythritol, by the Tollen’s Permuterm Subject Index 1639 Paterno-Buchi¨ reaction 1060 reaction 1193 peroxide, benzyl 853 and diradicals 1060 pentahelicene, and chirality 145 peroxides 870 See also intramolecular 1061 and steric crowding 145 hydroperoxides JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2058 SUBJECT INDEX

peroxides, acyl, from acyl halides peroxy-mercuration 917 Peterson olefination see Peterson 503 peroxyacids, from acids 1498 alkenylation with aldehydes 871 from acids, reagents 1498 petrochemistry, ketones 324 with aromatic compounds with aromatic compounds 674 pH, and hydrazines, with 878–879 and Baeyer-Villiger aldehydes or ketones 1115 with hydrocarbons 871 rearrangement 1378 and hydroxylamine, with peroxides, and addition of and dihydroxylation of alkenes aldehydes or ketones 1115 aldehydes to alkenes 981 1006 and solvent acidity 352 of polyhalo compounds to and epoxidation of alkenes and tautomerism 97 alkenes 1004 1010 phase transfer catalysis 474, 499, peroxides, and alkenes 910 oxidation of amines to amine 599, 1013 and anti-Markovnikov addition oxides 1504 alcohol oxidation with Cr(VI) 910 preparation 867 1447 and conjugate addition of with alkenes 904 alkenes with HX 911 boranes 967 with epoxides, and hydride alkylation of amides 528 and decarbonylation 889 shifts 1434 aminohydroxylation 1019 and Fenton’s reagent 865 with ketones 1378 and acyl cyanides 1257 and ferrous sulfate 865 peroxyesters 871 See also and ammonium salts 475 and halogenation 863 peroxides, acyl and carboxylate salt alkylation and Orton rearrangement 679 labeling 871 499 and oxidation of thioethers peroxyimidic acid, and dioxiranes and cations 477 1505 1013 and crown ethers 476 and radical coupling of alkanes with alkenes 905, 1014 and cryptands 476 874 peroxynitrous acid 865 and dehydrogenation 1455 and radical rearrangements persistent α-amino radicals 1125 and dihydroxylation 1006 1346 radicals 252 and enolate alkylation 576, 582 and radicals 840, 862 persulfate, potassium see and formation of alkyl halides and the Glaser reaction 876 potassium 535 and the Story synthesis 1332 PES (photoelectron spectroscopy), and halide ions 535 peroxides, cleavage 263 and alkenes 15 and HCN addition to alkenes cyclic 1056 and bond fixation 74 991 preparation of 1332 and carbocations 232 and hydroxylation of aromatic decomposition 840 and conformations 188 compounds 865 diacyl 262 and hybridization 15 and interfacial mechanism 476 and peroxide 262 and ionization potential 214 and ion pairs 476 from acyl halides 503 and methane 12–15 and Julia-Colonna epoxidation dialkyl 503 and multiple bonds 15 1016 diffusion rate of radicals 840 and orbitals 14 and microwave reactions 477 formation of radicals 840 and radical cations 15 and nitriles 600 from alkyl halides 503 and strain 214 and nucleophilic substitution from cycloaddition of singlet and the captodative effect 74 476 oxygen to dienes 1056 cyclobutadiene 73 and oxidation of amines 1492 from hydrocarbons 867, 870 pentalene derivatives 67 and permanganate oxidation of hydro see hydroperoxides spectrum, and nitrogen 13 alcohols 1450 hydrogen see hydrogen Petasis reaction 1202 and polar solvents 474 peroxide accelerated 1202 and preparation of carbonates with thiols 1509 and flow reactions 1202 501 alkenes and formic acid 1006 enantioselectivity 1203 and radicals 477 hydroperoxides 840 mechanism 1202 and rearrangements 537 nickel 873 Petasis reagent 1202 and sulfur ylids 1205 oxidation of thiols 1509 reactivity 1202 and tetracarbonylferrate peroxy-mercuration 917 structural variations 1202 alkylation 604 photolysis 327 with aldehydes or ketones 1202 and the Michael reaction 956 tert-butyl, and Sharpless with lactams 1202 and the Mills reaction 829 asymmetric epoxidation with lactones 1202 and thioether formation 507 1016 Peterson alkenylation 1191 and water 475 with alkenes 1006 and Me3SiCH2CO2Et 1192 and Williamson ether synthesis and bromine 1348 and silyl-Wittig reaction 1191 490 with Grignard reagents 734 aza- 1192 phase transfer catalysis, with HBr and alkenes 910 mechanism 1192 anhydrides from acyl with organometallic reagents modified, epoxide formation halides with carboxylic 735 1192 acid salts 1235 with sulfuryl chloride 853 structural modifications 1192 aryl halides with alkoxides 781 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2059

chiral 475, 576, 597 and tautomerism 100 phenylseleno esters 716 cleavage of ethers 540 and the enol form 101 phenylseleno ketones 716 CuCN and aryl halides 794 aromatization of cyclic ketones phenylseleno, leaving group in dehydrohalogenation 1312 1443 radical cyclization 974 diazotization of aromatic by electrolysis 674 phenylselenophthalimide 716 compounds 639 by Fries rearrangement 675 phenylselenyl chloride 716 ester hydrolysis 1220 carbonylation 669 phenylsilane, reducing agent Finkelstein reaction 535 deoxygenation 1572 1120 fluorination of alkyl halides phenols, from alkali fusion 781 phenylthio, leaving group in 535 allylic aryl ethers 1415 radical cyclization 974 for transesterification 1233 from aromatic compounds 674, phosgene, and dehydration of hydrogenation, aromatic 865 amides to isonitriles 1328 compounds 1523 from aryl diazonium salts 826 and Vilsmeier-Haack reaction α-hydroxylation of ketones from aryl ethers 496 663 1484 from aryl halides 779 formation of aryl carboxylic Michael reaction 956 and microwaves 780 acids 667 N-heterocyclic alkenes 475 flow reactions 780 formation of haloformic esters phosphonium salts 475 metal catalyzed 781 1106 quaternary ammonium salts with borane and a metal 780 preparation with flow reactions 475 phenols, from aryl sulfonic acids 337 reverse 477 781 reaction with alcohols 1106 thioethers, oxidation to from benzene and oxygen 780 with amines 1239 sulfoxides 1508 from boronic acids and H2O2 with carboxylic acid salts 1236 triphase catalysts 477 780 phospha-Brook rearrangement phase-vanishing solvent 1129 from esters 675 1438 phenacenes, and aromaticity 84 hydrogenation 1572 phospha-Friedel-Crafts acylation phenalene cation, resonance to cyclohexanones 1524 663 energy 61 to cyclohexenones 1524 phospha-Michael addition 977 phenalene radical, resonance nitration 631 enantioselective 977 energy 61 oxidation 1441 phosphate esters 505 phenalene, acidity of 61 to quinones, reagents 1459 phosphates, amination 714 and aromaticity 60 photochemistry 324 and chirality 138 phenalenol, and borane 1386 quenching in photochemistry conversion to amides 605 phenanthrene, and aromaticity 60 325 coupling with alkyl silanes 547 and bond fixation 60 thioalkylation 671 phosphatoxy radicals 1346 and bromine 60 with alkenes 916 phosphazenes, as catalysts 310 and Dewar benzene structures with boronates 594 phosphazides 1565 60 with formaldehyde and amines and reduction of azides 1565 and ozone 60 671 phosphazo compounds 1565 and partial bond fixation 60 with photoredox catalysis 780 phosphinates 637 bay region 60 phenonium ions 431 phosphine catalyst, with ketenes canonical forms 60 and electrophilic aromatic and aldehydes or ketones cyclization with singlet oxygen substitution 433 1261 1056 and isotope effects 433 phosphine oxides, and resonance resonance energy 60 and labeling 433 52 from stilbenes 1398 and NMR 432 and ylids 52 phenanthroline 937 and rate 431 by oxidation of phosphines phenofluor, and ether formation and solvolysis 432 1504 781 stable 432 chiral reduction, phenol-dienone rearrangement with alkyl halides 480 enantioselectivity 1586 1360 phenyl carbocations 230–231 conversion to thiophosphates phenol-keto tautomerism see phenyl radicals see radicals 1268 tautomerism phenyl radicals 263, 853 enantioselectivity 1587 phenols, acid catalyzed phenylenediamine, oxidative from alkenes 929 rearrangement of dienone cleavage 1472 reduction to phosphines, chiral 1360 phenylenes, as twisted compounds 1586 phenols, acidity 355 51 resolution 167 acyl, Fries-rearrangement 675 phenylhydrazine, with aldehydes with isocyanates 1259 2-allyl, by Claisen or ketones 1419 isotopic labeling 1260 rearrangement 1415 phenyllithium 115–116 mechanism 1260 and ether formation 494–495 aggregation state 248 phosphine-alkene ligands, chiral and Fenton’s reagent 865 phenylmagnesium bromide, and 311 and hydrogen bonding 109 X-ray 245 phosphine-catalyst, chiral 1054 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2060 SUBJECT INDEX

phosphines, alkylation 517 phosphonium halochromates alkanes 317 and Mitsunobu reaction 500 1449 alkenes 317 and the Reformatsky reaction phosphonium salts, by the and geometry 328 1153 Arbuzov reaction 1198 with alcohols 919 as chiral ligands in catalytic conversion to ylids 1194 allowed and forbidden reactions hydrogenation 1515 from alkenes 928 1049 as ligands 44 phase transfer catalysis 475 amines 317 by reduction of phosphine reduction to hydrocarbons 1585 from nitro compounds 1561 oxides 1586 suitable bases for ylid with cyclopropane 526 catalyst for Michael addition formation 1194 and [2+2]-cycloaddition 1057 956 with bases 1194 and actinometer 331 chiral, from phosphine oxides with organolithium reagents and auxochromes 318 1586 1194 and chlorosulfenation 872 conjugated addition 977 phosphoramides, and determining and chromophore 316 from alkenes 928 absolute configuration 154 and chromophore absorption anti-Markovnikov 929 phosphoramidites, preparation 318 from aryl halides 790 1268 and conjugated bonds 317 from phosphine oxides 1586 phosphoranes, selenium ylids, and decarbonylation 889 from phosphines 790 phosphorus and dehydrogenation 1446 oxidation to phosphine oxides vinyl, rearrangement 1407 and electromagnetic spectrum 1504 phosphorescence 322–323 316 polymer-bound, and Mitsunobu phosphorous, compounds, with and electron spectrum 316 reaction 500 aromatic compounds 637 and electronic transitions 314 vinyl 929 stabilization of carbanions 241 and exciplex formation 325 from alkynes 928–929 oxychloride, and from amides and excited states 318 with alkenes 928 720 and extinction coefficient 316 with alkyl halides 1194 pentabromide, with aldehydes and Hund’s rule 316 with alkynes 928 or ketones 1127 and hypsochromic shift 318 phosphino alkynes, from alkynes pentachloride 537 and nitrile reduction 1557 742 and electronic structure 16 and nitriles 1584 phosphiranes, divinyl, Cope with aldehydes or ketones and photolytic cleavage 320 rearrangement 1410 1127 and photosensitization 323 phosphites, and the Corey-Winter with amides 1435 and pinacol coupling, reaction 1316 with amides, Sonn-Muller¨ mechanism 1595 reduction of hydroperoxides method 1558 and quenching by phenols 325 1576 trichloride, with sulfonic acids and radical addition 1217 trialkyl, with acetals 501 1270 and singlets 316, 323–324 with sulfonic acids 1268 and carbanions stabilization and spectrophotometer 314 trimethyl, and Mislow-Evans 243 and the Frank-Condon principle rearrangement 1422 and optical activity 140 320 with alkyl halides 1198 and stereogenic atoms 183 and the Prins reaction 1215 with cyclic thionocarbonates chirality 183 and the Reed reaction 872 1316 inversion of configuration 183 and the Wittig reaction 1196 with halogens 1128 ligands, and ionic liquids 311 and triplets 316, 323–324 catalyst for Wittig reaction ylids see ylid and UV 314, 318 1199 phosphorylation, aromatic and visible light 314, 318 phospholene-1-oxides, with compounds 637 photochemistry, aromatic isocyanates 1259 photo-Fries rearrangement 676, compounds with aryl phospholes, and circumambulatory 680 iodides 879 rearrangement 1403 and CIDNP 676 aromatic ketones 325 phosphonate esters 505 flash photolysis 676 arylation of active methylene allylic 929 photobromination 857 compounds 820 and Horner-Wadsworth- photochemistry 164, 314–331, bathochromic shift 318 Emmons reaction 590 See also excited states, carbonates, methyl magnesium, 1198 photolysis, photolytic with ketones 1193 by the Arbuzov reaction cleavage, chemical processes 326 1198 photosensitization chlorination 850 from alcohols 504 acetylene excited state 319 choice of photosensitizer 323 vinyl, conjugate addition 979 alcohols 317 cleavage 326 amino, chiral 929 aldehydes 317 to radicals 326 conversion to amines 590 aldehydes with alkenes 981 and radicals 262 from phosphonates 1268 aldehydes, conversion to acetals conjugate addition 976 with alkyl halides 590 1102 cyclization 327 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2061

[2+2]-cycloadditions 1062 phosphorescence 322–323 photolysis 319 See also and Woodward-Hoffmann photoisomerization 326 photochemistry, photolytic rules 1063 photolysis of ketene 328 cleavage [3+2]-cycloadditions 1034 photoreduction 330 photolysis, and conjugate addition cycloaddition of oxygen to photosensitizer definition 323 969 dienes 1055 π → π* transitions 317 aniline ammonium salts 680 deactivation 325 promotion 322 aromatic compounds with aryl decarbonylation 327 to a dissociative state 320 halides 880 decarboxylation 684, 752, 754 properties of excited states 319 benzenes and Dewar benzenes decomposition 326 quantum yield 331 1395 of diazomethane 267 quenching 324 carbenes 727 dehalogenation, aryl halides photochemistry, reactions 313, diazoketones 1359 1570 326 1,4-diones 1333 dehydrohalogenation 1312 reactions, table 326 flash 331 dienes 317, 1432 rearrangements 326, 1400 of bromoform 269 dimerization 326, 330 cyclohexadienones 1433 laser flash 225 electronic excitation 316 reduction of cyclopropanes NBS and tosylamines 543 elimination 1273 1530 of cyclic sulfones 1331 energy cascade 321 reduction of nitro compounds of diazomethane 725 energy of light 314 1563 of ketene 328 ethers 317 reduction with silanes 1541 of ketones 328 ethylene, excited state 319 sensitization 326 of lactones 1331 excited state 314 singlet and triplet excited states of peroxides 327 of formaldehyde 319 319 of pyrazoles 1330 extrusion of nitrogen 1330 singlet states 1060 of pyrazolines 1330 flow reactions 337 σ → σ* transitions 317 of triazolines 1330 fluorescence 322 spin forbidden transitions 316 pyrocalciferols 1392 forbidden transitions 316, 320, SRN1 reactions 775 ring contraction of 323 steroid derivatives 1402 diazoketones 1364 formation of carbocations 413 sulfonyl-halo addition to photolytic cleavage 319 g and u transitions 316 alkenes 999 and the Franck-Condon ground state 314 suprafacial [1,3]-migrations principle 320 halogens and halogenation of 1406 energy cascade 320 alkanes 857 symmetry-forbidden transitions formation of radicals 320, 326 Heck reaction 812 316 Norrish type I 326 HOMO of cyclobutenes 1391 triplet states 1060 Norrish Type II 327 hydrogen atom abstraction 326, vinylcyclopropane of aldehydes 327 330 rearrangement 1407 promotion to a dissociative [1,7]-hydrogen shifts 1403 Wallach rearrangement 1436 state 320 photochemistry, internal wavelength of light 314 photolytic halogenation 847 conversion 321 Wigner spin-conservation rule photolytic hydroxylation 675 intersystem crossing 322 323 photonic devices 128 intramolecular rearrangement with acyl iodides 1252 photoorganocatalyst, and radicals 328 Wolff rearrangement 970 isomerization 328 1364–1365 photooxidant, acridinium 920 of azacrown ethers 329 photocyclization, dienynes 1392 photooxidation, of alcohols 1456 of azo compounds 329 photodimerization 326 of dienes 1055 of oximes 328 cyclopentenone 330 of methylarenes 1480 Jablonski diagram 321 photoelectron spectroscopy see photoredox amide formation 873 ketones 317 PES photoredox catalysis, formation of mechanism see mechanism photogeneration of phenols 780 mechanism 330 Vilsmeier–Haack reagents photoredox conditions, and nitrosation 711 1244 lactone formation 1027 Norrish Type I cleavage 326 photoinduced, benzyne click photoredox coupling, biaryls 805 Norrish Type II cleavage 327 reaction 774 photoredox thiol-ene reaction n → π* transitions 317 photoirradiation, Xenon lamp 879 953 n → σ* transitions 317 photoisomerization 326, 328 photoreduction, of ketones 330 of aryl alkenes 1398 azacrown ethers 329 photosensitization 323, 326, 379 of bicycloheptadienes 329 azo compounds 329 and electron transfer 325 of dienes 1389 hydantoin derivatives 329 and singlet oxygen 869 Orton rearrangement 679–680 of cyclooctene 328 of alkanes 874 Pauson-Khand reaction 986 oximes 328 of oxygen, with alkenes 868 phenols 324 photoisomers 26 Paterno-Buchi¨ reaction 1061 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2062 SUBJECT INDEX

photosensitized cycloadditions, pig liver esterase, and resolution and field effects 362 and diradicals 1062 169 and formation of enolate anions and triplets 1062 pinacol coupling 1594 575 photosensitizers 324, 1061, and Grignard reagent 1134 aniline 366 1480 and PEDOT 1596 benzoic acids 363 and [2+2]-cycloaddition 1060 and ultrasound 1595 carboxylic acids, table 363 and singlet oxygen 868 crossed 1595 cyanomethanes 363 choice of 323 enantioselectivity 1595 cyclopentadiene 63 cycloaddition of singlet oxygen reagents 1595 cyclopentadiene derivatives 64 to dienes 1056 flow reaction 1594 diketones 363 definition 323 imines 1595 fluorene 64 eosin 1056 reagents 1595 in DMSO 344 photoswitches 329 intramolecular 1595 indene 64 phase transfer 580 metal catalyst 1594 ketones 1171 phthalamic acid, hydrolysis 1093 photochemistry 1595 measurements 346 phthalate ion, rearrangement 685 mechanism 1595 naphthol, ground versus excited phthalazines, and asymmetric reagents 1594 state 319 dihydroxylation 1008 reversible 1595 nitriles 364 and dihydroxylation selectivity 1595 nitromethanes 240 1008–1009 syn selective 1595 of conjugate base in enolate phthalic acid, by oxidation of unsymmetrical 1594 anion reactions 579 naphthalene 1472 pinacol rearrangement 1354, 1363 α-proton of carbonyl phthalic anhydride, from and epoxidation 1500 compounds 579 naphthalene 1472 enantioselectivity 1354 of nitrile compounds 579 phthalides, Ing-Manske procedure mechanism 1354 resonance effects in carboxylic 530 migratory aptitudes 1341, 1354 acids 363 phthalimide, formation of amines of epoxides 1356 squaric acid 90 529 organocatalysts 1354 substituted benzoic acids 363 Gabriel synthesis 529 solvents 1354 table, type of acid 341–345 hydrolysis 530 stereodifferentiation 1354 tropone 65 Physical Constants of Organic supercritical water 1354 water 1171 Compounds 1620 pinacol, aza- 1596 pKb see pK, and base physical data, tables 1621 pinacolone 1500 planar conformation, physical processes, of excited and H2S clathrate 123 cyclopropane 202 molecules 323 clathrate compound 123 planarity, and annulenes 79 Physical Properties of Chemical formation 1354 and aromaticity 71, 83 Compounds 1620 X-ray as guest molecule 123 and benzene 50 physical properties, and Beilstein pinacols see diols and C=C bonds 220 1618 pinacols 1354 and carbocations 413–414 and diastereomers 158 α-pinene, with borane 935 and cyclobutadiene complexes pi-stacking 113 pinene, enantiomers 935 75 Piancatelli rearrangement 959 Pinner synthesis 1106 and heptalene 67 picene 85 piperidine, and and methanoannulenes 80 picolinium halochromates 1449 cyclopropylcarbinyl and paracyclophanes 50 picosecond absorption halides 445 and resonance 49 spectroscopy 416 Pisum sativum, oxidation of and resonance contributors 47 and solvolysis 416 hydrocarbons 1476 annulenes 87 picosecond optical grating Pitzer strain see strain distortion from 80 calorimetry 1073 pK indicator, 2,4-dinitroanilinium of ylids 53 picrates 116 ion 352 Planck’s constant 3, 314 picric acid, and arenium ions 611 o-nitroanilinium ion 352 plane of symmetry, and chirality and complex formation 116 pK, and bases, table 348 136 picryl iodide, and resonance 49 and carbocation formation 231 plane polarized light see light Pictet-Spengler reaction, and and conformation 368 plane polarized light 157 BINOL 655 and hydrogen bonding 366 and enantiomers 149 enantioselective 655 and indicators 352 plane, mirror plane, and chirality isoquinolines 655 and proton transfer 350 136 organocatalyst 655 and resonance 365 and enantiomers 136 tetrahydroisoquinolines 655 and UV 366 platinum complex, and Pictet–Spengler isoquinoline carbocations 231 cycloalkynes 216 synthesis 655 pKa, and acids 340–347 resolution alkenes 168 Piers hydrosilation 1541 and aldol condensation 1173 platinum compounds, and asymmetric 1545 and deprotonation 575 atropisomers 143 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2063

Pleurotus ostreatus MTCC-1801 polyleucine, and epoxidation porphycenes, tautomerism 102 1456 1016 porphyrins, and rotaxanes 127 PMHS (polymethylhydrosiloxane) polymer bound, and acylation of tautomerism 102 1550 amines 1241 positional isomers, aromatic, pnictogens 92 Beckmann rearrangement 1375 stability 622 podands 120, 476 catalyst, Suzuki-Miyaura postulate, Hammond 291 poisoning, and catalytic coupling 801 potassium alkyls 244 hydrogenation 1513 Cinchona alkaloids 1008 potassium aryls 244 chiral, in asymmetric catalysis Cope elimination 1308 potassium ferricyanate 724 1515 osmium tetroxide, and potassium fluoride, in acetic acid, of catalytic hydrogenation 1513 dihydroxylation of alkenes formation of acyl fluorides polar Diels-Alder reactions 1044 1006 1251 polar solvents see solvents OsO4 1006 potassium hydride, with polar solvents, and hydrogen oxazaborolidine, and reduction silyl-thiols 506 bonding 470 1544 potassium hydroxide see KOH and reactivity 390 phosphonate esters 1198 potassium in sodium 1599 polarity, and cyclooctatetraene 77 quaternary ammonium salt potassium ions, and ambident inductive and field effects 21 1016 nucleophiles 481 methyl radical 853 reagents 504 and crown ethers 120 solvent 474 conversion of acids to amides potassium permanganate see polarity, solvent see solvent, 1242 permanganate polarity siloxanes, and and oxidation of diols 1006 polarizability, and conformation transesterification 1233 and oxidative cleavage of 190 reduction 1559 alkenes 1470 and HSAB 480 sulfoxide, and Swern oxidation dihydroxylation of alkenes and nucleophilicity 480 1451 1005 and optical activity 13 TPAP, oxidation of alcohols dihydroxylation of alkenes, of halogens 643 1454 ultrasound 1006 polarization, and microwaves 334 polymer supported, carbodiimides potassium persulfate, and bond, of conjugated carbonyls 1242 Boyland-Sims oxidation 895 catalysts 977 674 effects 113 dienes 1053 and hydroxylation of aromatic inductive and field effects 21 iodoarylboronic acid 1244 compounds 674 topological 70 ligands 566 potassium superoxide see polarized bonds 17 Mitsunobu reagents 500 superoxide polarized light, circularly 157 oxidizing agents 1449 potassium thiocyanate, with a and asymmetric synthesis peroxy acids, and sulfur-transfer agent 508 166 Baeyer-Villiger potassium plane 157 rearrangement 1379 tri-sec-butylborohydride polarized transition state 409 synthesis 1244 see Selectrides poly(ethylene) glycol see PEG sulfur ylids 1205 potassium, ammonia, reduction of poly(ethylenedioxy)thiophene see polymeric acid catalyst 1230 aromatic compounds 1524 PEDOT polymerization 236 and SRN1 reactions 775 polyacenes, and annellation 61 and Free radical addition 897 and the acyloin condensation and Kekule´ structures 61 and haloacylation of alkenes 1599 and UV 61 1005 in ammonia, and Birch angular and linear 61 and hydroformylation 989 reduction 1524 anthracene 61 and radicals 263 potential energy, and reactions phenanthrene 61 halo-haloacylation of alkenes 283 triphenylene 61 1005 potential, ionization see polyalkylation, Friedel-Crafts of heptalene 67 ionization potential alkylation 652 polymers, and supercritical carbon Povarov reaction, azadienes 1054 polyaromatic compounds see dioxide 392 oxo analog 1054 aromatic compounds paraformaldehyde 1259 powdered Grignard reagents 747 polyenes, cyclization, cation 944 polymethylhydrosiloxane 1582 powdered metals 748 radical 944, 974 and reduction of amides 1582 PPh3 and CCl4, with alcohols UV 317 reducing agent 1120 537 polyethylene glycol see PEG reduction 1550 PPh3 and I2, solvent-free, and polyhalo compounds, addition to polyphosphoric acid, and microwave irradiation 538 alkenes 1004 Friedel-Crafts alkylation preformed iminium salts 1123 polyhydrogen fluoride–pyridine, 654 preparative LC, and diastereomers fluorination 1251 polystyrene resins, catalysts 477 168 with alkenes 910 porous crystalline material 311 and resolution 168 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2064 SUBJECT INDEX

pressure, and kinetics 300 prochiral ketones, reduction of and lactams 351 and substitution reactions 418 1542 and Marcus theory 356 catalytic hydrogenation 1514 definition 184 and pK 350 pressure, high see high pressure product identification, and and principle of imperfect pressure, high, and dipolar mechanism 293 synchronization 351 transition states 478 product quantum yield 331 and radicals 869 and microwaves 812 product spread 442 and resonance 351 and partial molal volume 478 proline esters, as catalysts 310 and solvents 351 and reactivity 390, 478 promotion of electrons 9 hydroxypropanoic acid 351 and steric hindrance 478 and fluorescence 323 transition state 356 and transition states 478 propargylic compounds, proton-shift tautomerism 100 and volume of activation 478 isomerization 909 proton-transfer reactions, and Horner-Wadsworth-Emmons propargylic radicals 256 diffusion control 350 reaction 1198 propellanes, and geometry 212 mechanism 350 pressure, versus rate constant and SN2 reactions 456 and hydrogen bonding 350 418 and strain 212 and in-in isomers 351 Prevost reaction 1006 X-ray crystallography 212 and out–in isomers 351 mechanism 1007 propeller shaped carbocations 233 intramolecular 350 Woodward modification 1007 propene, and hyperconjugation 95 to carbon 351 Prilezhaev reaction, epoxidation from cyclopropane, and entropy protonated cyclopropane 1339 1010 286 oxetanes 1213 primary quantum yield 331 propiolic acids, from alkynes 988 protonation, enantioselective, primary sources, literature 1607 propynyllithium, with Me3SiCl enolate anions 704 principle of conservation of orbital 552 of diazo compounds 467 symmetry 1045, 1063 protection-deprotection, and of radical ions 1525 principle of imperfect solvent free reactions 395 protonic acids, and Friedel-Crafts synchronization 351 protection, of alcohols as ethers acylation 659 principle of increasing electron 492 and reverse Friedel-Crafts demand 425 protein catalysts, Baylis-Hillman alkylation 681 principle of least motion 1525 reaction 1150 protonolysis, of alcohols 235 principle of microscopic protic solvents 469 of alkenes 235 reversibility 291, 1215 proton acceptor, bases 339 of boranes, with carboxylic Prins reaction 1213 proton affinity, and basicity 347 acids 1522 and electrochemistry 1215 and basicity of proton sponges of iminium ions 235 and oxocarbenium ions 1214 367 α-protons, and enolate anions 575 and photochemistry 1215 imines 1097 and the Sommelet-Hauser and the ene reaction 1215 proton donors, acids 339 reaction 835 and transition metals 1215 proton NMR see NMR as a leaving group 608 cyclic mechanism 1214 proton sponges 349, 367 enolizable 703 cyclization 1214 and base strength 367 prototropic rearrangements 698, halogenation of alkenes 1004 and helicene 144 1335 iodide promotion 1214 and proton affinity 367 prototropy, keto-enol tautomerism ketones 1214 and β-lactams 1262 701 Lewis acid catalysts basicity of 367 proximity-induced Diels-Alder 1214–1215 bis(amino)fluorenes 367 reaction 1037 Markovnikov’s rule 1214 bis(amino)naphthalenes 367 Pschorr reaction 879 mechanism 1213 bis(amino)phenanthrenes 367 intramolecular Gomberg oxocarbenium ions 1213 bis(dimethylamino)naphthalene reaction 831 pericyclic mechanism 1214 349 pseudo first order, kinetics, SN2 reversible 1215 bis(tetramethylguanidino) reactions 405 stereoselectivity 1213 naphthalene 349 rate constant, and solvent structural variations 1215 quinolino[7,8-h]quinolines 349 acidity 354 with allenes 1214 quinoquinolines 367 reactions 299 with dienes 1214 Schwesinger 349 pseudo Pauson-Khand reaction with oxetanes 1213 vinamidine 349 985 priority rules, Cahn-Ingold-Prelog proton transfer, and acidity 350 pseudo-axial 204 system 149–152 and alkynes 351 pseudo-equatorial 204 prismane 1414 and amides 351 pseudo-first order, SN1 reactions and strain 212 and amines 351 412 Ladenburg formula 1063 and chloroform 351 pseudo-rotation 50 probes, SET 253 and cyclohexane-1,2-diols 351 pseudoasymmetric carbon 159 procedures, acyloin condensation and HCN 351 Pseudomonas oleovorans GPo 1598 and keto-enol tautomerism 701 1486 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2065

Pseudomonas putida Gpo1, and the Doebner modification pyrophosphate, synthesis of 122 oxidation of hydrocarbons 1188 pyrroles, alkylation 515 1476 basicity 63, 367, 372 and aromaticity 62 Pseudomonas putida,and catalyst for hydrolysis of and atropisomers 143 dihydroxylation of anhydrides 1219 and circumambulatory aromatic compounds 1010 derivatives, aminomethylation rearrangement 1403 pseudorotation 195 671 atropisomers 143 and conformations 203 from amino halides 515 B-substituted 842 and cyclophanes 51 from dihydropyridines 1445 basicity 63, 372 and equilibrium 195 from diynes and heterocyclic canonical forms 63 Pshcorr reaction, mechanism 833 carbenes 1078 carboxylates 1392 publications: notes and from nitriles with alkynes 1078 conversion of enamines 742 communications 1609 from pyrroles 1073 cyclopropanation 1073 puckered conformations 204 hydroxymethyl, by Boekelheide electron potential map 62 pulsed ultrasound 332 react 1383 formylation 665 Pummerer rearrangement 1350, in rotaxanes 130 Friedel-Crafts alkylation 652 1603 iodoborane 937 from azapentadienyl cations enantioselectivity 1603 SEAr reactions 623 1392 isotopic labeling 1603 with amide bases 823 Paal-Knorr pyrrole synthesis mechanism 1603 with carbon dioxide and metal 1114 Pummerer-sila 1603 catalyst 668 resonance energy 63 purity, optical 173 pyridinethiol, and tautomerism SEAr reactions 623 push–pull effect 74 101 with diazo compounds 1081 and radicals 255–256 pyridinium chlorochromate see with supercritical carbon pybox catalyst, and amination PCC dioxide, and Bacillus 516 pyridinium compounds, leaving megaterium 668 pybox ligands, chiral, and flow groups 466 with vinyl triflates 741 chemistry 337 pyridinium dichromate see PDC pyrrolidines, derivatives, insertion pyracyclene, and Stones-Wales pyridinium ions, ionic liquids 393 reaction 729 rearrangement 1399 pyridinium phenolbetaine 474 from allenes and azides 1031 paratropic 87 pyridinium salts 466, 474 from haloamines 515, 1433 pyramidal inversion 138 See also ionic liquids 393 from hydroxamic acids 1359 inversion pyridinophanes 50 Hofmann-Loffler¨ reaction pyran 58 pyridinyloxy derivatives 631 1433 and aromaticity 59 pyridnyl Grignard reagents 882 vinyl, from alkene–amides 931 pyranose compounds, and pyridones, and tautomerism 101 N-alkylation 478 tautomerism 103 pyrimidylindoles 650 from cyclopropyl tosylimines pyrans, from diketones 1103 pyrocalciferols, electrocyclic 1407 pyrazoles, and diradicals 1330 reagents 1392 via aza-Wittig reaction 1202 extrusion of nitrogen 1330 photolysis 1392 pyrylium ions 58 from diketones 1116 Pyrococcus furiosu 1547 Friedlander¨ quinoline synthesis pyrazolines, conversion pyrolysis 510 See also flash 1113 cyclopropanes 1032 vacuum pyrolysis pyrylium salts, leaving groups extrusion of nitrogen 1330 biphenylenes 1399 466 from keto esters 1116 cyclobutane 209 reaction with amines 466 pyrenes, and complex formation cyclopropanes 1358 121 dehydrohalogenation 1313 QMC see MO Calculations and aromaticity 82 mechanism 1297 Quadricyclane 1062 pyrenophanes 50 of amine oxides 1307 quadrivalent stereogenic atoms pyridine-2-thione, and of ammonium carboxylates 138 tautomerism 101 1241 quantum mechanics, and pyridine-HF, and acetals or ketals of ammonium salts 1305 hyperconjugation 94–95 488 of carboxylic acids 1304 and molecular mechanics 205 pyridines, alkylation with of cyclic peroxides 1332 quantum Monte Carlo 37 carboxylic acids 880 of cyclobutane 209 quantum yield, and radicals 844 and radicals 880 of cyclopropane 208 definition 331 mechanism 880 of esters 1303 primary 331 pyridines, and aromaticity 59 of homoallylic alcohols 1328 product 331 and chlorination of alcohols of hydrazonium salts 1325 quasi-Favorskii rearrangement 441 of xanthate esters 1304–1305 1363 and Collins reagent 1448 pyrolytic elimination 1273, 1296 quasiadiabatic collapse 332 and resonance 34 and Bredt’s rule 1298 quasiclassical electrostatic and rotaxanes 130 and Hofmann’s rule 1298 attraction 32 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2066 SUBJECT INDEX

quaternary ammonium salts see and first order reactions 414 polyenes 944 ammonium salts and organocuprates 558 SOMO–LUMO interactions quaternary ammonium salts, and radicals 845 974 molten 476 and rearrangement 1338 tin-free 973 phase transfer catalysis 475 and SE1 reactions 691 to aldehydes 1217 polymer-bound 1016 and SN1 reactions 414 with imines 1217 thermal stability 476 and SN2 reactions 407 radical ions 265, 420 quaternary salts, and exhaustive and solvolysis 416 acepentalenes 265 alkylation 513 and the Wittig rearrangement and alkali metals 266 quaterphenyl, from dibenzo[fg, 1384 and Birch reduction 1525 op]tetracene 1398 of configuration, of migrating and formation of Grignard quenching, and kinetics 300 group during reagents 749 in photochemistry 324 rearrangement 1338 and oxidation of Cathecols and quinazolines, and tautomerism out–in isomers 182 hydroquinones 1460 103 radialene-like 62 and semiquinones 265 quinhydrones 116 radialenes 61 and solvent cage 421 quinidine nitrate 1521 radiationless processes 322 cation 266 quinolines, and decarboxylation radical anions, and azoxy azulenes 266 684 compounds 763 nonplanar 266 by dehydrogenation 1446 and Birch reduction 265 from Na 1525 Friedlander¨ quinoline synthesis and ESR 763 ketyls 265 1113 and SRN1 775 silylenes 265 from indoles 1073 and SRN1 reactions 775 radical pairs 848 SEAr reactions 624 energy levels 775 formation, nitration of aromatic quinolino-quinolines, bases 349 radical cations 850, 1445 See also compounds 633 quinolino[7,8-h]quinolines, proton radical ions mechanism, and the Wittig sponge 349 aminium 860 rearrangement 1384 quinoloquinolines 349 and PES 15 radical, addition, to alkenes, and quinone-bridged calixarenes 120 catalysts, Diels-Alder reaction tetrahedral mechanism quinones, and 1038 847 addition–elimination methane 15 abstraction of atoms 263 mechanism 446 radical chain mechanism 1475 abstraction, transition state 845 and aromatization 1443 radical clocks 264, 850, 1346 acyloxylation 872 mechanism 1443 radical cyclization 971 activity 856 biphenylene 77 and MO calculations 974 radicals, acyl see acyl radicals by dyotropic rearrangement and [1,4]-hydrogen transfer acyl 842, 890 1437 1403 from aldehydes with by oxidation, of aromatic and aryl radicals 973 transition metals 842 hydrocarbons 1489 and Baldwin’s rules 971 conjugated, rearrangement of hydroquinone 1459 and boranes 969 842 of phenols 1459 and dienes 897 acyloxy 263 complexes 116 and flow reactions 975 acyloxylation 871 from isonitriles and alkynes and heterocycles 975 addition 281, 896 1264 and hydrogen transfer 972 to alkenes 263, 843, 903, from naphthalene or anthracene and iodolactonization 973 970 1489 and ring size 972 to alkynes 970 stability 619 and samarium (II) 973 to imines 1217 via Bergman cyclization 1395 and tributyltin dimer 972 to oximes 1217 with dienes 1036 and tributyltin hydride 969, 972 and photochemistry 1217 quinoquinolines, as proton and trifluoroborates 975 enantioselectivity 1217 sponges 367 formation of heterocyclic rings polyhalo compounds to 973 alkenes 1004 R and F values, table 386 formation of isoquinolines 975 reversible 899 R values, and σ values 387 formation of lactams 973 radicals, aldehydes with R-camp, chiral ligand 1515 formation of lactones 973 conjugated ketones 1217 racemates 135 radical cyclization, Grignard alkenyl, and radical cyclization and resolution 135 reagents and CoCl2 974 973 and substituted cyclohexanes kinetics 972 alkoxy 271, 840–851 198 LUMO–HOMO interactions alkoxyalkyl 259 racemic mixtures see racemate 974 alkoxyarylaminyl, X-ray 257 racemic mixture 147 mechanism 971 allylic 254–255, 862 racemization, and amines 140 metal catalysis 974 and electron diffraction 254 and carbanions 242 of iodocarbonyls 974 and resonance 852 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2067

rearrangement 852 and halogenation of alkenes and stability 299 stereoisomers 256 992 and step-scan time-resolved alternant hydrocarbons 69 and halonitroso compounds infrared 251 amide 842 1002 and Stephens–Castro coupling amidyl 975 and α-heteroatoms 851 817 α-amino, persistent 1125 and Hofmann-Loffler¨ reaction and strain 853 aminopyrenyl 257 1433 and symproportionation 939 aminoxyl 258 and hybridization 258 radicals, and the Etard´ reaction aminyl 975 and hydroamination 929 1481 radicals, and addition of aldehydes and hydrogen bonding 256 and the Hammett equation 853 to alkenes 981 and hydrogen transfer reactions and the Hunsdiecker reaction of thiols to alkenes 922 843 848, 887 radicals, and AIBN 841, 862 and hydrogenation 1517 and the Kolbe reaction 885 and akene halogenation 995 and hyperconjugation 94, and the Orton rearrangement and alkene halogenation 995 254–255, 261 680 and alkylation 477 and inhibitors 844 and the Pauli principle 251 of pyridine 880 and inorganic molecules 251 and the Schmidt reaction 1374 and arylation, active methylene and Jacobsen-Katsuki and the Strecker synthesis 1212 compounds 820 epoxidation 1017 and the Wittig rearrangement and aryldiazonium salts 833 and mass spectrometry 251 1384 and atom transfer reactions 843 and metal catalyzed and tributyltin hydride 263 and autoxidation 868 acyloxylation 871 and triethylboranes 969 and aziridine formation 1024 and NBS 862 and ultrasound 478 and azulenyl nitrones 252 NMR 252, 254 and unpaired electrons 251 and Barton reaction 1434 emission 253 and UV 254, 862 and bis(decarboxylation) of and Norrish type I reactions anomeric effect 259 dicarboxylic acids 1475 1331 anti-Markovnikov addition to and bond energy 32 radicals, and organocalcium alkenes 970 for atom abstraction 849 reagents 248 radicals, aryl 826–827, 832, 854 bond rotation 260 and organolithium reagents 751 and CIDNP 846 and boranes 969 and oxidation of cathecols and and diazonium salts 826 and captodative effect 256 hydroquinones 1460 and disproportionation 846 and carbenes 261, 727 of thiols to disulfides 1510 and radical cyclization 973 and CH oxidation of aryl and oxidation–reduction 1441 canonical forms 846 methyl 1481 and oxidative decarboxylation coupling 845 and chromotropic spin traps of carboxylic acids 1474 ipso attack 854 252 and oxygen autoxidation 868 meta selectivity 854 and CIDNP 253, 421, 1348 and ozonolysis 1467 ortho/para selectivity 854 and conjugate addition 969 and peroxide formation 870 partial rate factors 854 and [2+2]-cycloaddition 1059 and peroxides 840 resonance 846 and cyclopropyl alkynes 256 and phase transfer catalysis 477 radicals, arylation 879 and decarbonylation 889 and photolytic cleavage 320 of arenediazonium salts 832 and decarboxylative and photoreduction 330 of aromatic compounds 879 halogenation 886 and polyene cyclization 944 radicals, as intermediates 294 and decomposition of peroxides and proton transfer 869 atom abstraction 844 840 and push–pull effect 256 atom transfer 845, 897 and decyanation 760 and quantum yield 844 reactions 842 and dienes 897 and racemization 845 azo compounds 262 and diselenides 863 and radical clocks 850 benzoyl 263 and electron withdrawing and rearrangement of benzylic 254, 852, 862 substituents 853 N-nitroaniline 677 bond dissociation energy and and enantioselectivity 845 and resonance 255 reactivity 855 radicals, and ENDOR 252 and ring expansion 850, 1358 radicals, bridged 847 and ESR 256, 421, 847, 1348 and selenyl halides 863 and CIDNP 848 and ESR/EPR 251–252 radicals, and SET mechanisms and stereochemistry 847 and formation of Grignard 253, 420 isotope effects 848 reagents 748 and silanes 862 radicals, bridgehead 260 and Grignard reactions 257, and sodium/ammonia 760 reactivity 853 1134 and solvation 843 radicals, bromine 263 with alkyl halides 554 and Sonogashira coupling 817 butenyl 850 and halo-alkenes, cyclization and spin states 252 by electrolytic methods 263 971 and spin trapping 252 by hydrogen atom abstraction and halo-ketones 1359 and SRN1 mechanism 775 330 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2068 SUBJECT INDEX

radicals, bromine (Continued) from alkyl halides 851 addition of alkanes to alkenes by photochemical cleavage 326 from alkyl hypochlorites 939 by thermal cleavage of 841 Diels-Alder reaction 1044 peroxides 261 from azo compounds 840 halogenation of allylic C-centered 257, 263 from diazonium salts 840 hydrogen 864 caged pair 1383 from Free radical addition to hydroboration 740 captodative 255 alkenes 896 initiation 859 carbon 223 from ketones 262 propagation 859 chain mechanism, and SRN1 from organotrifluoroborates and termination 859 reactions 775 UV 338 radicals, methane 17 chain reaction 843 from radicals 262 methyl 259 characterization 251 generation of 261 and ESR 258–259 chiral 259 generation of radicals for IR 259 chlorine 841, 848 addition to alkenes 970 polarity 853 cleavage of 263 geometry 259 Michael addition 956 complex with solvent 857 half-life 251 migrating groups in concentration of 252 halogen 262 rearrangements 1348 conjugate addition 969 abstraction 851 1,2-migration 1358 Cope rearrangement 1412 rate of H abstraction 852 migratory aptitudes 1348 coupling 263, 845 with allylic and benzylic N-containing 258 of alkyl halides 563 hydrogens 862 neophyl 1346 and the Kolbe reaction 885 halogenation 862 neutral 855 crystals 257 of carboxylic acids 709 nitric acid, with alkanes, and cubylcarbinyl 1347 homocubyl 1347 radicals 711 cyclization 421 hybridization 258 nitroxide 256, 259, 261 cyclobutylcarbinyl, hydrazyl 256 nitroxyl 256, 1463 rearrangement 850 hydrogen abstraction 846 oxidation of alcohols 1452 cyclopropanes, addition and rearrangements 1346 nucleophilic 853, 902 reactions 907 from alkanes 849 organometallics, Michael cyclopropyl 260 from alkenes 852 addition with alkenes 964 cyclopropylcarbinyl 264, 850 rate 848 oxidation to carbocations 265 rate of rearrangement 850 transition state 848 oxygen 975 radicals, decarboxylation 874 radicals, hydrogen atom transfer ozone and hydrocarbons 1476 decomposition 263 973 pentadienyl 255 delocalization of migrating aryl hydroxy 840 pentenyl 850 groups 1347 imidoyl 842 persistent 251–252 destruction 842 imines with boranes 1165 phenyl 263, 848, 853 detection of intermediates 294 in aqueous media 258 phosphatoxy 1346 diffusion rate 840 inhibitors 844 photochemical cleavage 262 dimerization 254 galvinoxyl 969 photoorganocatalyst 970 dimethylenecycohexane-1,4- initiation 839, 845, 922, 929, planar versus pyramidal 259 diyl 261 981 polar transition states 853 diphenylpicrylhydrazyl 256, addition of sulfonyl halides to polyene cyclization 974 299 alkenes 999 polymerization 263 disproportionation 263 azo compound 841 probes 421 dissociation energy 258 boranes 841 propagation steps 843, 897 table 258–259 boron compounds 841 propargylic 256 dissociation, and photo-Fires triethylborane 970 push–pull 255 rearrangement 676 intermediates 477 radical 873 E/Z isomers 255 Grignard reagents, and O2 radical clock reactions 264 electrophilic 845, 902 734 radical clocks 1346 elimination 263, 1297 ion-radical pair, and SNAr radical cyclization see radical enaminyl 1125 reaction 770 cyclization fast radical reaction 850 ions, and cyanation 724 rate of H abstraction and fate of 261 isomerization 898 structure 852 fluorination 861 ketenyl 842 rate of rearrangement 264 formation 840 ketones, from carboxylic acids radicals, reaction characteristics in UV-flow reactors 338 1257 843 fragmentation of carbenes 274 kinetics of radical chain radicals, reactions, arylation 800 free 223 reactions 843 formation of aryl, nitriles 673 free, from carbanions 250 lifetimes 251–252, 850, 1348 and σρ relationship 389 radicals, from AIBN 841 radicals, mechanism 839, 865, transition metal promotion from aldehydes 262 868, 1475 853 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2069

with cyclopropanes 908 triplet 261 and ring-closing reactions, table with dienes 897 vinyl, and radical cyclization 286 radicals, reactivity 843, 854–856, 973 and the Hammett equation 381 901 E/Z inversion barrier 255 carbene with alkenes 1069 and structure 849 radicals, with alkanes 849 ester hydrolysis 384 and substrates 848 with alkenes 843, 846, 852, 912 first order 302 in aromatic solvents, complex metal catalyzed 970 hydrolysis 383 formation 856 with alkyl halides 848 lactone formation 287 with aromatic compounds 854 with alkylsilanes 843 pseudo first order, and solvent radicals, rearrangements 264, with allenes 904 acidity 354 282, 851, 972, 1345–1346 with aromatic compounds, second-order 302 and CIDNP 1348 mechanisms 845 versus pressure 418 and ESR 1348 with benzylic hydrogens of rate controlling step 298 and isotopic labeling 1347 aromatic compounds 852 rate determining step, acetal and stability 1348 with dienes 899, 912 hydrolysis 487 of aryl groups 1346 with haloamines 860 and E1 mechanism 1280 radicals, reduced to carbanions with tributyltin hydride 843 benzidine rearrangement 1423 265 radii, hydrogen bonds 109 E1cB mechanism 1283 reduction 843 radioactive, carboxylates 295 E2 reactions 1274 to a carbocation 749 iodide, and SN2 reactions 407 haloform reaction 758 with silanes 843 nitriles 295 multi-step reactions 299 with tributyltin hydride 972 radiolabels, C14 296 protonation of alkynes 916 resonance stabilized 846 Raman spectroscopy, and SN1 reactions 410 ring expansion of halo-ketones carbocations 233 rate enchantment, and neighboring 1359 and conformations 188 groups 432 rotation barrier 260 and hydrogen bonding 109 and cyclopropylmethyl groups selectivity 854 and intermediates 294 436 selectivity of hydrogen and methyl neighboring groups and high pressure 391 abstraction 849 438 and PEG 391 SH1 mechanism 845 and the Fries rearrangement of the oxy-Cope rearrangement SH2 mechanism 845 677 1409 1,2-shift 1346 laser, and nonclassical solvolysis 436 silicon containing, X-ray 258 carbocations 435 solvolysis of cyclobutyl 437 singlet 261 nanosecond time resolved 677 rate factors, partial 619, 629 solid 256 of nitric acid 632 rate law 299 solvent cage 554, 751 Ramberg-Backlund¨ reaction 1316 and frequency factor 303 solvents and reactivity 856 and episulfones 1317 and half-life 301 spectroscopic analysis 251 mechanism 1317 and kinetics 297 spin traps 256 order of halogen reactivity and mechanism 297 stability 250, 254–255, 903, 1317 and molecularity 298 1346 Ramberg-Backlund-type¨ reaction, and solvent isotope effects 307 and steric hindrance 255 halo-sulfides 1317 and steady state 299 and substitution 255 RAMP, hydrolysis 1097 first-order 301 and conjugation 256 Raney nickel see nickel methods for determining radicals, stable 251, 258 Raney nickel, and desulfurization kinetics 300 stereoelectronic effects 853 1589 pseudo first-order 300 steric effects 256 and desulfurization of rate-determining step 298 strain and reactivity 853 dithioketals 1110 rate of reaction, acetolysis 433 structure 251 and hydrogenation 1513 alkyl halides, hydrolysis, table structure and reactivity 849 rapid injection NMR 555 378 β-substituents, and rate acceleration, and microwave with aqueous ethanol 378 rearrangements 1347 chemistry 335 with ethanol 377 substitution 844 See also Diels-Alder reaction 1038 amide hydrolysis 377 substitution rate constants 285 See also and chiral compounds 134 succinimidyl 865 kinetics and enantiomers 158 TEMPO 256 acid–base reactions 355 and ionic strength 412 termination steps 842, 897 addition carbenes, to alkenes and leaving groups 1093 thermal cleavage 261 1069 and mass-law effect 412 thiyl 262, 890 and cyclopropylcarbinyl and medium 390 triaryl 255 radicals 264 and microwave chemistry 334, trimethylenemethane 260 and Marcus theory 298 478 triphenylmethyl 254–255 and mechanism 297, 303 and neighboring group effects stability 855 and phenonium ions 432 431 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2070 SUBJECT INDEX

rate of reaction, acetolysis SN2 reactions 450, 454 nucleophilic 280 (Continued) and allylic substrates 452 photochemical 313 and neighboring group and solvent effects 470 photochemical, table 326 participation 422 SNAr reactions 777 proton-transfer 350 and nucleophiles 461 solvolysis 379 pseudo first-order 300 and nucleophilicity 461 of alkyl bromides 450 second-order 297 and phenonium ions 431 alkyl halides 379 synthesis, table 458–459 and radical clock reactions substituent effects on solvolysis thermodynamically controlled 264–265 428 290 and resolution 171 substitution 695 very fast, kinetics 301 and resonance 452 salt effects 690 ReactIR 294 and salt effect 412 tritium exchange in aromatic reactivity, alkene metathesis and SN1 reactions 410–411, substitution 630 1429 450 rate of solvolysis, of alcohols 378 alkenes versus alkynes 901 and SN2 reactions 405, 407, rate retarding substituents 454 alkyl halides with ethanol, table 449 rate, of diffusion, and high 377 and solvation 461 pressure 391 and cavitation 477 and solvents 471 and reactivity 390 and conformation 379 and solvolysis 432 rate, of exchange, SN2 reactions and conformational and steroids 380 407 transmission 380 and structure 450 rate, of hydrogen abstraction, and electrical effects 375 and temperature 303 halogen radicals 852 and field effects 375 and the ortho effect 389 rate, of inversion, SN2 reactions and high pressure 390, 478 and the Smiles rearrangement 407 and ionic solvents 393 837 rate, of ionization and solvents, and medium 390 and the tetrahedral mechanism table 471 and microwaves 477 1090 sulfonate esters, solvent effects and rate of diffusion 391 rate of reaction, arenium ion 471 and resonance 375 mechanism 610 Rauhut-Currier cyclization 1151 and ring strain 524 aromatic substitution 627 Rauhut–Currier reaction 1445 and ρ values 382 aryl radicals, regioselectivity, aza- 1445 and σ values 382 table 855 re/si nomenclature 186 and steric effects 377 common-ion effects 412 reaction conditions, alkene and substrate structure 449 Cope elimination 1307 metathesis 1429 and tetrahedral intermediate decarboxylation 755 catalytic hydrogenation 1514 376 Diels-Alder reactions 1044 reaction coordinate 285 and the Hammett equation 381 electrophilic aromatic reaction enthalpy 1523 and ultrasound 477 substitution 625 Reaction Index of Organic aromatic compounds 614, 626 elimination 1297 Syntheses 1629 catalytic hydrogenation enantiomers 135 reaction rates see rate of reaction 1524 hydrazines, with aldehydes or reactions, and Hammond reactivity, functional groups and ketones 1115 postulate 291 reduction 1512 hydrogen abstraction by and molecularity 298 hydride reagents 1533 radicals 848 and steady state 299 in supercritical carbon dioxide hydrolysis of alkyl halides 379 by type of compounds 392 of esters 379 synthesized 1640–1643 in water 391 hydroxylamine, with aldehydes by type of compounds of aromatic compounds 626 or ketones 1115 synthesized, classification of groups, in SN1 reactions, ionization and B strain 378 1642 table 456 nitration of aromatic class e and class n 1096 of groups, in SN2 reactions, compounds 632 diffusion-controlled 285 table 456 of chlorination and nitration, electrophilic 280 of radicals 854 table 612 enantioselective 165 reactivity, of radicals 856 of cyclopropylcarbinyl radical first-order 297 and structure 849 rearrangement 850 gas-phase, and kinetics 301 substrate variation 848 ortho/para/meta substitution, gas-phase, kinetics 301 oxidation, of aromatic side aryl radicals 854 homodesmotic 39 chains 1473 partition factor 610 intermediates 286 quantitative treatments 380 radicals, and inhibitors 844 isodesmic 39 radicals 855, 901 SEAr reactions 615 kinetically controlled 290 solvent polarity 390 SN1 reactions, and alkyl kinetics of fast reactions 301 reactors, microwave 335 tosylates 452 multi-step, rate determining Reagents for Organic Synthesis and B strain 451 step 299 1629 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2071

reagents, alcohol reduction 1571 for, α-hydroxylation of ketones peroxyacids from acids, alcohols, from hydrocarbons, by 1485 reagents 1498 oxygen insertion 1477 for hydroxylation of pinacol coupling, aldehydes, deoxygenation hydrocarbons 1476 enantioselectivity 1595 1578–1579 for isonitriles, dehydration of reagents, reduction of alkenes oxidation to carboxylic acids amides 1327 1519 1495–1496 for McMurry coupling 1597 of alkyl halides 1568 amines, by reduction of nitro for α-oxidation of ketones of amine oxides 1586 compounds 1558 1487 of azoxy compounds 1586 from nitro compounds 1560 for oxidation of alcohols to of conjugated alkenes 1528 and CH oxidation of aryl carboxylic acids of diazonium salts 1587 methyl 1481 1492–1493 of esters to alcohols 1548 and Hofmann rearrangement of aldehydes to carboxylic of ethers 1573 1370 acids 1495–1496 of imines 1554 and oxidation of amines to of aldehydes to carboxylic reagents, self-immolative 164 amine oxides 1504 esters 1497 sulfides, by reduction of anhydrides, reduction to of amines 1492 sulfoxides 1590 aldehydes 1551 of aromatic side chains 1473 thiols, oxidation to disulfides by oxidation of hydrocarbons, of thioethers 1505–1508 1510 reagents 1476 for oxidative cleavage of transfer hydrogenation, conversion to alkenes, alkenes 1470 reduction of imines 1554 mechanism 1302 of alkenes 1472 1,2-rearrangements 1348 dealkylation of amines 1592 of aromatic compounds 1472 isocyanides 1384 dealkylation, of sulfonamides of diols 1463 of alkyne anions, ab initio study 1592 for pinacol coupling 1594 1349 deoxygenation, of aldehydes or for preparation of thiocarbonyls 1,4-rearrangements 1349 ketones 1578–1579 1109 1,5-rearrangements 1348 diols, oxidation to lactones reagents, for reduction of 1,6-rearrangements 1348 1494 aldehydes or ketones to [2,3]-rearrangements 1385 elimination of dihalides to alcohols 1532 rearrangements, acyl aziridines alkenes 1319 of alkenes to alkanes 1520 1408 enantioselective reduction 1545 of conjugated alkenes 1526 phosphorus ylids 1308 esterification of aldehydes with of conjugated carbonyls 1533 rearrangements, alkenes and alcohols 1497 of nitriles 1558 photosensitized oxygen esters, reduction to aldehydes of ozonides 1466 868 1551 of sulfonate esters 1575 with alcohols 917 reduction to alkanes 1575 reagents, for reductive alkylation rearrangements, alkyl azides 1378 ethers, cyclic, oxidation to of aldehydes or ketones rearrangements, alkyl groups, lactones, reagents 1488 1119 Hofmann-Martius reaction reduction of esters 1579 from reduction of oximes 1562 680 reagents, for allylic and benzylic hydride 1533 rearrangements, alkyl, and oxidation 1478–1480 chiral additives 1544 Friedel-Crafts reactions for aromatization 1442–1443, hydrogenolysis, of esters 1576 680 1445 α-hydroxylation of ketones from ammonium salts 680 for Beckman rearrangement 1483 from aniline ammonium salts 1375 imine reduction 1554 680 for conjugate reduction 1527 Katritzky pyrylium–pyridinium photolysis of aniline ammonium for dehydration of amides, to method 1585 salts 680 isonitriles 1328 ketones, deoxygenation rearrangements, allenes 909 to nitriles 1327 1578–1579 rearrangements, allylic 441, 694 for dehydration of oximes to miscellaneous, conjugated ammonium salts 1421 nitriles 1325 alkenes 1529 carbenes 726 for dehydrogenation of amines for oxidation of alcohols conversion to allenes 1319 to nitriles 1460 1455–1458 and acyl addition of allylic for epoxidation of alkenes 1011 nitro compounds, reagents for boranes 1145 for formation of acylals 1104 reduction 1563 and allylic radicals 852 for halogenation of ketones 704 oxidation of alkenes to ketones and propargyl systems 444 for hydrolysis of C=N 1499 and SNi′ reactions 444 compounds 1097 of alkynes to diketones 1501 formation of allenes 444 of dithioacetals and of Cathecols and halogenation 863 dithioketals 1110 hydroquinones 1459 SN2′ reactions 444 for α-hydroxylation of carbonyl of hydrazones 1462 amino-Cope 1409 compounds 1483 of phenols 1459 ammonium salts 835 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2072 SUBJECT INDEX

rearrangements, and addition of rearrangements, carbene 1349 halogen from N-haloamides alkyl halides to alkenes and allylic insertion 725 679 1004 to carbene 1364 halogenation of alcohols 537, and addition–elimination hydrogen shifts 1349 539 mechanism 446 rearrangements, carbene–carbene hiscotropic 1357 and allylic carbocations 452 1364 Hofmann 1370 and benzoylnorephedrine rearrangements, carbocations mechanism 293–294 379 236, 604, 917, 939 [1,5]-homosigmatropic 1419 and carbenes 274 and deuterium labeling 1339 1,3-hydride, and greater 1344 and carbocations 724, 1351 Friedel-Crafts alkylation hydride 1344 and cyclopropylmethyl groups 651 reduction of alkyl halides 437 rearrangements, Carroll, Claisen 1568 and diazotization of amines rearrangement 1417 hydroboration 736 1339 catalytic Wagner-Meerwein hydrogen as a migrating group and diradicals 1347 1353 1340 and formation of carbocations cationotropic 1335 in oxidation with PCC 1448 1336 Chapman 1435 intermolecular, definition 1335 and formation of nitrenes 1336 circumambulatory 236, 1403 internal abstraction 1349 and Friedel-Crafts alkylation Claisen 1414 intramolecular 1370 650 rearrangements, Cope see Cope definition 1336 1,3- and greater 1344 rearrangement photochemical 328 and ions 1343 Cope 1408 ion pairing 1343 and isotope effects 1339 cubane 1431 ipso carbon 633 and methyl group participation cubycarbinyl radicals 265 Ireland-Claisen, Claisen 438 Curtius 1364, 1371 rearrangement 1417 and neighboring group cyclohexadienones 1360 Ireland-Claisen, mechanism 423 cyclopropyl propargylic enantioselectivity 1417 and ozonolysis of alkenes 1467 alcohols 1357 α-ketols 1360 and phenonium ions 431 cyclopropylcarbinyl, in ionic Kimel-Cope, Claisen and racemization 1338 liquids 1357 rearrangement 1417 and SN1-type processes 1338 metal catalysts 1357 lithio ethers 1384 and solvolysis 438 degenerate 1337 lithio-epoxide 523 and the Jacobsen reaction 685 Demyanov 1357 long range 1344 and Whitmore 1,2-shifts 1336 di-π-methane 1432 Lossen 1372 rearrangements, anionic oxy-Cope di-π-methane, regioselectivity Meerwein-Eschenmoser 1409 1432 Claisen, Claisen anionic Snieckus-Fries 677 Diels-Alder reactions 1039 rearrangement 1417 aryl carboxylate ions 684 diene-alcohols 1405 Meinwald 1355 aryl group, transition state 1347 dienone–phenol 1360 metal catalysts 1355 aryl triazenes 679 dienone–phenol, mechanism Meisenheimer 1383 aza-Claisen 1418 1360 memory effects of migrating aza-Cope 1409, 1418 divinylcyclobutanes 1410 groups 1342 aza-Payne 498 double bond 699 methylenecyclopropanes 1357 aza-Piancatelli 959 dyotropic 1436 Meyer-Schuster 444, 1367 aza-Wittig 1385 electrocyclic 1389 metal catalyzed 1368 BtoO 1385 and orbital symmetry 1396 migrating group 1335 Baeyer-Villiger 1378 electrophilic 282, 1335, 1349 migration origin 1335 Bamberger 836 electrophilic allylic, geometry migration terminus 1335 Beckmann 1326, 1338–1369, of 694 migratory aptitude, H versus 1375 [2,3]-enantioselectivity 1422 alkyl versus aryl 1341 migratory aptitudes of groups energy 1350 migratory aptitudes 1340 1341 enolene 1419 Mislow-Evans 1422 benzidine 1422 epoxy–alcohols 497 multiple 1,2-shifts 1353 benzil-benzylic acid 1361 Eschenmoser-Claisen, Claisen N-nitroso groups 678 mechanism 1361 rearrangement 1417 N-nitrosoanilines 678 benzyl ammonium salts 834 Favorskii 1361 nature of the migration 1337 benzyltrimethylammonium mechanism 1362 Neber 1369 1383 Fischer-Hepp 678 and intermediate isolation σ-bond, metal catalyzed 1431 Fries 675–676 294 boron-to-carbon 1385 Fritsch–Buttenberg–Wiechell neopentyl carbocations 1339 Brook 1437 1313 nitriles from oximes 1326 C → O 1378 rearrangements, Grovenstein- nitro groups 677 CtoN 1369 Zimmerman 1353 nitrogen ylids 835 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2073

nitrogen-to-oxygen 1330 retro-Claisen 1415 reduction of aldehydes and nitroso amides 833 Schleyer adamantization ketones 1533 nucleophilic 282 1353 reduced mass, and mechanism mechanism 1336 Schmidt 1376 305 rearrangements, of aldehydes, acid semipinacol 1355 reducing agents, alkoxyaluminum catalyzed 1359 sequential 1,2-shifts 1344 hydride 1536 of ammonium salts, base rearrangements, sigmatropic see for ozonides 1466 induced 1381 sigmatropic hydrogen gas 1120 of aryl oximes 836 sigmatropic 402, 1399 phenylsilane 1120 of carbanions 250 configuration of migrating polymethylhydrosiloxane 1120 of carbenes 272–273, 1068 groups 1405 sulfur 1591 of carbocations 225, 759, 894, definition 1400 reductases 1530 913 [1.2]-sigmatropic hydrogen reduction 282 direction of rearrangement shift 1357 acyl halides, reagents 1549 1337 [2,3]-sigmatropic 835, 1420 aldehydes and ketones, steric of diazo alkoxides 1366 biocatalysts 1421 hindrance 1533 of diols, migratory aptitudes Wittig 1421 alkyl halides, rearrangements 1341 sila-Pummerer 1603 1568 of esters 675 Smiles 837 SN1-like mechanism 1569 of hydroperoxides to ketones Sommelet 1382 and chiral ligands 1544 1381 Sommelet-Hauser 835, 1382 and Grignard reactions 1132 of ketones, acid catalyzed 1359 Stephens 835 and Hantzsch esters 1528 mechanism 1360 stereochemistry of migrating and selectivity 1511 of nitrenes 277 groups 1338, 1340 asymmetric 1542 of protonated cyclopropanes Stevens 835, 1381, 1422 asymmetric, benzoylformates 1339 Stieglitz 1378 164 of radicals 264 Stone-Wales 1399 borane reagents 1539 β-substituents 1347 strained cage molecules 1431 boranes, chiral additives 1544 of vinyl epoxides, metal tert-pentyl carbocation 1337 Cannizzaro reaction 1540 catalysts 1355 Tiemann 1372 carbonyls with sodium in ortho substitution 1383 transannular 1345 ethanol, mechanism 1537 steric effects 1383 hydrogen shift 1349 conjugate, with silanes 1528 Orton 679 and alkyl groups 1345 conjugated carbonyls, reagents peroxides 679 Truce-Smiles 838 1533 photochemical 679 vinylcyclopropane 1406 definition 1439 Overman 1418 vinylcyclopropane, metal dissolving metal 1524 oxa-di-π-methane 1433 catalyzed 1407–1408 ease of reduction of functional oxy-Cope 1409 von Richter 834 groups 1511 rearrangements, para-Claisen rearrangements, enantioselective 1544 1415 Wagner-Meerwein see functional group reactivity σ-participation 1352 Wagner-Meerwein 1512 Payne 497 Wagner-Meerwein 1352, 1377 gain of hydrogen or loss of phenol-dienone 1360 and carbocations 1351 oxygen 1439 photochemical 1400 Wallach 1436, 1600 hydrogen transfer 1541 Piancatelli 959 Willgerodt 1350 isocyanates 1105 pinacol see pinacol with σ-participation 1352 Katritzky pyrylium–pyridinium pinacol 1354 Wittig 590, 1384, 1422 method 1585 enantioselectivity 1354 “wrong way” 1348 nitriles to methyl, with terpenes migratory aptitudes of groups Wolff 1262, 1363 1566 1341 Reaxys 1614, 1617, 1640–1643 nitro compounds, reagents stereodifferentiation 1354 and Beilstein 1619 1563 propargyl 444 recognition, molecular 121 reduction, of alcohols, reagents prototropic 698, 1335 recrystallization, fractional, and 1571 Pummerer 1350, 1603 diastereomers 168 of aldehydes and ketones, metal quasi-Favorskii 1363 and resolution 168 hydrides 1533 radical 282, 851, 972, 1345 rectus, and stereogenic centers with metals 1537 and hydrogen abstraction 186 of alkyl halides, reagents 1567 1346 recyclable, catalysts, alkene of amides, reagents for 1581 and isotopic labeling 1347 metathesis 1429 of azides, metals 1564 of aryl groups 1346 Mitsunobu reagents 500 of aziridines 1584 and stability 1348 Red-Al 1534 of boranes 1387 migrating groups 1348 functional group reactivity of conjugated alkenes, Reilly-Hickenbottom 680 1533 1,4-redciton 1527 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2074 SUBJECT INDEX

reduction, of alcohols, reagents reductive cleavage, of transesterification 1233 (Continued) cyclopropanes 1530 Ullmann reaction 797 catalytic hydrogenation 1526 reductive coupling 1593 unsymmetrical ketones 582 Hantzsch ester 1527 Reed reaction 872 registry Number, Chemical hydride reducing agents Reed reaction, mechanism 872 Abstracts 1617 1527 references from Organic Reilly-Hickenbottom metal catalysts 1527 Syntheses 400 rearrangement 680 reagents 1526, 1528 Reformatsky reaction 560, 1152, Reimer-Tiemann reaction, and aryl transfer hydrogenation 1527 1262 aldehydes 666 of esters 1574 and activated zinc 1152 and CCl4 668 reagents 1548, 1575 and chiral auxiliaries 1153 heteroaryl aldehydes 666 of hydrazones, reagents 1555 and chiral catalyst 1153 regioselectivity 666 of ketimines, reagents 1555 and dialkylzinc reagents 1152 with sulfuric acid to give of ketones, diastereoselectivity and Grignard reaction 1153 aldehydes 1552 1545 and hydrolysis 1153 relationships, Hammett-Brown of nitriles, hydride reagents and phosphines 1153 627 1558 and solvents 1152 σ-relationships, and radical of oximes, reagents 1555 and sonochemistry 333 reactions 389 of ozonides, reagents 1466 and transition metals 1152 relative configuration 159 of radicals 843 and ultrasound 1152 relay catalysts 311 of radicals, with tributyltin and Wittig reaction 1153 remote dehydrogenation 1446 hydride 972 and zinc source 1152 remote oxidation 1477 prochiral ketones 1542 hydrolysis 1153 Reppe carbonylation 982 1,4-reduction of conjugated intermediates 1153 residual dipolar coupling 160 alkenes 1527 metal catalysts 1152 resins, polystyrene 477 sulfonates, reagents 1572 solvents 1152 resolution 139 sulfoxides and sulfones 577 with carboxylic esters 1153 amine salts 169 type of 1510 X-ray of intermediates 1153 amino acids-boric acid 167 with alanes 1540 refractive index, and optical and brucine 167 with ammonium formates 1541 activity 156 and carbenes 171 with boranes, enantioselectivity regiochemistry, elimination 1288 and chiral additives 170 1540 Fries rearrangement 676 and chiral crown ethers 168 with PMHS 1550 of elimination 1288 and chiral recognition 169 with silanes 1541 of the Heck reaction 812 and cholic acid 169 Wolff-Kishner 1577, 1584 regioselectivity, acylation 1253 and chromatography 168 reductive alkylation 1118, 1122 addition, to cyclopropanes 906 and crown ethers 167, 169 amines, from nitro compounds aldol condensation 1174 and cryptands 169 1561 alkene reactivity 902 and cyclodextrins 169 and formic acid 1119 alkenes with alcohols 916 and differential absorption 169 and the Wallach reaction 1121 and ambident nucleophiles 478 and enzymes 169 enantioselectivity 1122 and hydroboration 933 and ephedrine 167 Hantzsch dihydropyridines and steric effects 481 and esterases 169 1119 9-BBN and alkenes 934 and fractional crystallization of alcohols 1105 benzyne formation 773 166–172 reductive amination 1118 condensation of esters and and fractional distillation 168 amine dehydrogenase 1120 ketones 1255 and GC 168 and hydrogenolysis 1119 definition 478 and mandelic acid 169 and platinum-nanowires 1120 Diels-Alder reactions 1040 and morphine 167 and the Eschweiler-Clarke dihydroxylation of alkenes and pig liver esterase 169 procedure 1121 1008 and preparative LC 168 and the Wallach reaction 1121 electron donating versus and rate of reaction 171 enantioselectivity 1121 withdrawing 622 and Sphingomonas flow reactions 1120 formation of arynes 778 pauchimobilis 172 Hantzsch ester 1122 Friedel-Crafts acylation 662 and strychnine 167 hydrogenase 1120 Friedel-Crafts alkylation 652 and sublimation 170–171 Leuckart reaction 1121 Friedel-Crafts formylation and synthesis 161 metal catalysts 1119–1120 664–665 biocatalytic, and flow reactors of aldehydes or ketones, halogenation of ketones 705 337 reagents for 1119 of unsymmetrical ketones biochemical processes 169 organocatalysts 1121 706 calixarenes 167 reagents 1118–1119 Mannich reaction 1123 chiral sulfoxides 1507 reductive carboxylation, of Reimer-Tiemann reaction 666 conversion to diastereomers alkenes 982 SEAr reaction 614, 619 167 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2075

deracemization 172 and aryl halides 46 of carbonate 42 green, of alcohols 171 and basicity 366 pyridine 34 resolution, kinetic 147, 169, 171 and benzene 34 rules of 46 See also kinetic resolution and bond angles 48 rules of stability 47 and alkenes 171 and bond distance 48 σ bonds 34 dihydroxylation of alkenes 171 and bond order 33 stability, enolate anions 579 and epoxidation of alkenes 171 and calculations 36 stabilization, and the resolution, mechanical 170 and canonical forms 33 captodative effect 74 and heptahelicene 170 and captodative effect 256 structures, fulvalenes 68 resolution, metal complexes 146 and carbanions 239, 243 retention of configuration, anions methods of 166–172 and carbocations 235, 452, 486 243 of alkenes 167 and charge separation 47 retention of migrating group of crystals 170 and Dewar structures 33 during rearrangement of enantiomers 135 and dimethyloxosulfonium 1338 of sulfur compounds 140 methylid 1205 retention, and chlorination of of trans-cyclooctene 168 and dimethylsulfonium alcohols 441 phosphine oxides 167 methylid 1205 and elimination–addition spontaneous 171 and diradicals 47 reactions 449 resonance 33 and electron density 48 and neighboring group resonance contributors, and and electronegativity 47 participation 427 planarity 47 and electrons 46 and phenonium ions 432 resonance effects 48 and enolate anions 240, 895 and SN1 reactions 417 and acidity 363 resonance, and hyperconjugation and SN2 reactions 406 and substituent effects 454 226 and SNi reactions 440 and σ values 386 and hyperconjugative stretching retro-aldol condensation 751, 756 electrostatic scale 38 95 retro-Barbier reaction 1130 resonance energy 34 See also and hypophosphorus acid 52 retro-Buchner¨ reaction 1070 energy and MO theory 34 retro-Claisen condensation 1254 ab initio calculations 38 and nonequivalent canonical retro-Claisen rearrangement 1415 acenes 85 forms 47 retro-[3+2]-cycloaddition 1031 and aromatic compounds 60 and orbitals 34 retro-Diels-Alder reaction 1043, and aromaticity 63 and oxocarbenium ions 1089 1047 and cross conjugation 44 and paracyclophanes 49 and thermal extrusion of carbon and dendralenes 45 and phosphine oxides 52 monoxide from ketones and fused aromatic compounds and phosphorus ylids 1194 1324 60 and π-bonds 46 retro-ene reaction, and pyrolysis and hybridization 41 and pK 365 of homoallylic alcohols benzene 37–38 and planarity 47, 49 1328 bond 64 and proton transfer 351 retro-Grignard reaction 1130 butadiene 40 and push–pull effect 256 retro-hydroformylation 989 cyclic 61 and radicals 255, 846 retropinacol rearrangement, and cyclopentadienide ion 63 and rate of reaction 452 Wagner-Meerwein furan 63 and reactivity 375 rearrangement 1352 phenalene radical and cation 61 and steric effects 48 reverse Brook rearrangement pyrrole 63 and strain 48 1438 thiophene 63 and sulfoxides and sulfones 52 reverse Claisen condensation 757 resonance, allylic and the Hammett equation 381 reverse Cope elimination 1308 carbanion/cation/radical and the mesomeric effect 48 reverse dienone–phenol 43 and unpaired elections 47 rearrangement, mechanism allylic carbocation 441 and vinyl chloride 42 1361 amine oxides 52 and wave equations 34 reverse Friedel-Crafts alkylation and 1,3-dipoles 1028 and ylids 52 see Friedel-Crafts and allylic carbanions 694 resonance, aryl diazonium salts reverse Friedel-Crafts alkylation and allylic carbocations 452 824 681 and allylic cations 898 carboxylate anion 684 reverse Gatterman-Koch reaction and allylic radicals 852 chorobenzene 46 683 and amines 365 Dewar structures 49 reverse phase transfer catalysis and aniline 48 energy and canonical forms 47 477 and anthracene 49 enolate anions 1172 reverse-Brook rearrangement and arenium ions 608 integral 38 1437 and aromatic compounds 35, interaction, substituents, reversibility, alkene reaction with 49 arenium ions 615 radicals 898 and aryl diazonium salts 823 naphthalene 34 microscopic 291, 1095 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2076 SUBJECT INDEX

reversible Diels-Alder reaction and the Stevens rearrangement rotamers, and conformers 188 1043 1381 and E2 reactions 1278, 1291 pinacol coupling 1595 aryl azides 1372 definition 187 radical addition 899 carbenes 1073 rotating-frame nOe spectroscopy reviews, annual 1623 cyclic ketones 1366 see ROESY annual, literature 1622 cyclopropylmethyl carbenes rotation barrier see barrier journals, table 1623 1359 rotation barrier, of radicals 260 of the literature 1622 halo ketones 1359 strained aromatic compounds rhodium catalysts 308–309 lactones 1437 219 and decomposition of of alkyl azides 1372 rotation, and catenanes 129 diazoalkanes 272 of aromatic rings 1024 and α 135 and the Reformatsky reaction of cyclic ketones 1366 and π-bonds 10 1153 Tiffeneau-Demyanov 1357 C—S, and chirality 244 deuteration of aromatic ring opening, cyclopropyl 1397 in ethane, energy barrier 190 compounds 630 cyclopropyl cations 1397 molar see molar rotation diazoalkane cyclopropanation cyclopropyl, metal catalyzed observed see observed rotation 1068 599 of plane polarized light 133 haloacylation of alkenes 1005 metathesis 1431 restricted, and atropisomers nitroso compounds and of [2+2]-cyclobutanes 1431 143 isocyanates 764 thermal, of cyclobutene 1393 and chirality 145 with acyl halides 1315 ring size, and entropy 286 and cis/trans isomers 219 with nitrosamides 1309 and lactone formation 286 specific see specific rotation Rhodococcus erythropolis SET1, ring strain, and bond energy 32 rotational transitions, and hydrolysis of nitriles and reactivity 524 spectroscopy 316 1100 energy and hyperconjugation rotaxane ligands 311 ribbons, molecular 128 96 rotaxanes 127–128, 130 riboflavin and alkene Ring Systems Handbook 1621 and chirality 147 isomerization 909 ring-chain tautomerism see and fullerenes 128, 131 ring bond order 64 tautomerism and isomers 128 ring closure, and entropy of ring-closing metathesis see and ligand exchange 128 activation 286 metathesis and Mobius¨ strip mechanisms Baldwin’s rules 288 ring-in-ring complexes 128 128 dig nomenclature 288 rings, common, strain 215 and molecular shuttles 130 disfavored 289 large, strain 215 and molecular switches 128 favored 289 medium, strain 215 and NMR 130 Friedel-Crafts acylation 660 small, strain 215 and porphyrins 127 metathesis 1424 Ritter reaction 1257 and stoppers 130 reactions, and rate constants, and microwaves 1258 and transitional isomers 128 table 286 and tautomerization 1257 as inclusion compounds 130 tet nomenclature 288 and the Beckmann as photonic devices 128 ring contraction, acid catalyzed rearrangement 1377 beads and stations 130 1356 ionic liquids 1258 bistable symmetric 128 diazoketones 1359 metal catalysts 1258 chiral 130 Favorskii rearrangement 1361 microwaves 1258 copper (I)-complexed 131 photolysis of diazoketones organocatalysts 1258 cucurbit[8]uril 132 1364 steric hindrance in nitriles 1258 hetero 131 ring current 54 Robinson annulation reaction inclusion compounds 130 and alkenes 55 1179 liquid crystals 128 and anisotropy 56 and Mannich reaction 1179 synthesis of 128 and annulenes 83 enantioselective 1179 triply threaded 128 and benzene 55–56 organocatalysts 1179 rotocatenanes 131 and cyclophanes 56 Robinson annulation-like reaction rotors, molecular 130 antiaromatic systems 56 1184 π-route, to nonclassical induced 54 Rodd’s Chemistry of Carbon carbocations 426 paramagnetic 56 Compounds 1625 rubidium alkyls 244 ring current, benzocyclobutene ROESY, and π–π interactions 113 rubidium aryls 244 52 Rosenmund catalyst, alkynes, and rules, and conformations 3n 189 ring expansion, acid catalyzed hydrogenation 1516 and diastereomers 2n 159 1356 catalytic hydrogenation 1516 of resonance 46 and metathesis 1430 Rosenmund reduction, of acyl stability of resonance forms and radicals 850, 1358 halides 1549 47 and Steven’s rearrangement Rosenmund-von Braun reaction ruthenium–salen complex, 1381 779, 793 catalyst 1017 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2077

ruthenium catalysts, and sandwiches, metal multi-decker SciFinder 1607, 1613, 1631–1635 metathesis 1426 66 limitations 1631 cycloisomerization of enynes saponification 1219 research topic hits 1631 1403 sawhorse diagrams 189 searches 1631–1635 oxidative cleavage of alkenes scale of nucleophilicity 464 use of 1633 1470 scale of reactivity, electrophilic α-scission 271 oxidative cleavage of alkynes aromatic substitution 626 scoopy reactions 1200 1471 of electronegativity 18 Scopus 1642 scavenger resins 1429 solvent nucleophilicity 472 SE1 reactions see substitution and Tischenko reaction 1602 scandium, and fullerenes 92 SE1 reactions, and Ruziˇ ckaˇ cyclization 1257 scavenger resins, and ruthenium decarboxylation 752 catalysts 1429 SE1 reactions 693, 696 s-character, and acidity 368 SCF method, and aromaticity 59 and isotope effects 691 and bond angles 28 Schiemann reaction 647, 828 and kinetics 692 and bond distance 26, 452 intermediates 829 and proton transfer 630 and bond energy 30, 32 Schiff base–chromium complex and racemization 691 and bond length 31 954 and solvent effects 692 and carbanion stability 238, Schiff bases, addition of HCN and sterochemistry 691 241 1212 effect of substrate 695 and hyperconjugation 95 catalyst 995 SE1 reactions, mechanism 613, and strain 208, 241 chiral 1140, 1212, 1508 691 S-alkylation 533 epoxides with and decarbonylation 683 S-alkylisothiouronium salts 497 organometallics 572 and decarboxylation 683, 685 s-cis dienes 1036 formation of 1112 and first order kinetics 691 s-trans dienes 1036 hydrolysis 1097 decarboxylation 755, 757 sacrificial hyperconjugation 96 organometallics reagents, with SE2 reactions 907 See also Sadtler Research Laboratories, imines 1164 substitution spectra 1621 reduction to amines 1553 and decarboxylation 752 Sakurai reaction 966 Schlenk equilibrium 245–246, effect of leaving group 696 allylsilanes, with aldehydes or 1133 effect of solvent 696 ketones 1148 Schleyer adamantization 1353 effect of substrate 695 aza reactions 967 Schmidt reaction 1373, 1376 organomercury compounds, palladium catalyst 966 acid catalysis 1373 effect of leaving group salen–metal complexes, and and hydrazoic acid 1117 696 epoxidation 1017 and microwaves 1117 SE2 reactions, mechanism 608 salen, cobalt 489 and nitrilium ions 1374 decarboxylation 755 salt effects, and kinetics 412 formation of lactams 1374 SE2 reactions (back) 688 and SN1 reactions 470 intramolecular 1373 SE2 reactions (co-ord) mechanism of lithium perchlorate 471 mechanism 1374 690 salt free phosphonium ylids migratory aptitude 1373 SE2 reactions (cyclic) mechanism, 1194 of azide ketones under radical Stille coupling 718 salts, ammonium see ammonium conditions 1374 SE2 reactions (front) 688 salts synthetic variation 1373 SEAr reactions see substitution salts, and SN1 reactions 470 Schmidt rearrangement 1376 SEAr reactions, activating groups enamine, and alkylation 587 and the Beckmann rearrange 617–618, 621 Meisenheimer 769 1376 and aromatic sulfonation 640 Meisenheimer-Jackson 769 Scholl reaction, Friedel-Crafts and leaving groups 628 samarium (II), and radical arylation 657 Baker-Nathan order 618 cyclization 973 intramolecular 657 deactivating groups 617, 622 samarium in acetic acid, and metal catalysts 657 electron releasing groups desulfurization 884 Schotten-Baumann procedure 617–618, 621 samarium iodide, with dinitriles 1227 electron withdrawing groups 1584 acylation of amines 1239 617, 622 ring expansion of cyclic Schrodinger¨ equation 3, 9 furan 623 ketones 1366 Schwartz’s reagent 938 fused heterocyclic systems 624 SAMP, hydrolysis 1097 reduction of amides to halogen substituents 617 Sanderson scale of aldehydes 1553 hetarynium ions 623 electronegativity 18 Schwesinger proton sponges 349 isoquinoline 624 Sandmeyer reaction 645, 827–828 See also bases, proton mechanism 608 mechanism 827 sponge meta substitution 615 sandwich compounds see SCI see Science Citation Index naphthalene 622 metallocenes Science Citation Index (SCI) ortho substitution 615 sandwich interactions 113 1614, 1625, 1635, 1637 ortho/para ratio 618 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2078 SUBJECT INDEX

SEAr reactions, activating groups Selectrides, functional group semibenzilic mechanism 1363 (Continued) reactivity 1535 semi-buckminsterfullerenes 92 para substitution 615 reduction of aldehydes and semibullvalene, and Cope pyridine 623 ketones 1535 rearrangements 1413 pyrrole 623 selenides, aryl, preparation 785 and homoaromatization 1413 quinoline 624 reduction with triaryltin hydride and strain 1413 rate of reaction 615 884 semicarbazide, with aldehydes or regioselectivity 614, 619 selenides, diaryl 510 ketones 1117 SET mechanism 628 from arenediazonium salts with semicarbazones, and Wolf-Kishner thiophene 623 arylselenenol 785 reduction 1577 indole 624 selenides, formation of selenones from aldehydes or ketones searching the literature 1630 1508 1117 SEC reactions, mechanism 690 oxidation to selenoxides or hydrolysis 1097 seco-acids 1231 selenones 1507 reduction to amines 1563 second order, Beckmann preparation 510 semidines 1422 rearrangements 1326 selenium, and carbonylation of semiempirical calculations 36 rate constants 302 amines 764 semihydrogenation 1516 reactions, kinetics 298 selenium compounds 506 metal free 1517 reactions 297 selenium dioxide, allylic oxidation semipinacol rearrangement 1355 secondary isotope effects of alkenes, mechanism semiquinones, radical ions 265 306–307 1482 semirubin, and hydrogen bonding in substitution reactions 456 and allylic oxidation 1481 112 secondary orbital interactions and dehydrogenation 1446 sequence rules, absolute Diels-Alder 1040 and ene reaction 1482 configuration 149–152 secondary overlap of orbitals, and Sharpless method for allylic serial publications, irregular, table Diels-Alder reaction 1051 oxidation 1482 1624 secondary sources, literature 1607 α-oxidation of ketones 1487 SET (single electron transfer) seeding method 171 and hypervalent iodine 1487 249 Selectfluor 534, 539, 707, 994 mechanism 1487 alkylation of enolate anions and amide formation 1258 oxidation, and [2,3]-sigmatropic 578 fluorination of aldehydes or rearrangement 1482 and Grignard reagents with ketones 705 selenium transfer reagents 1510 alkyl halides 554 fluorination of alkenes 997 selenium ylids 53 and organocalcium reagents with alkenes 911, 1003 chiral 1205 248 selectivity, aldehydes, with selenium, and aromatization 1443 and SRN1 reactions 421 organometallics 1138 with Grignard reagents 738 mechanisms 420 See also aldol condensation 1174 seleno carbonyls 716 mechanism alkene metathesis 1428 seleno esters, by carbonylation and aldol condensation 1171 and catalytic hydrogenation 821 and chain reactions 420 1519 from diselenides and acyl and coupling 567 and reduction 1511 halides 1227 and oxidation–reduction carboxylic acids, reduction with selenoamides 1126 1441 hydride reagents 1547 and transamidation 1238 and radicals 420 catalytic hydrogenation of from amides 1238 formation of Grignard alkenes 1515 selenocarbonates 1105 reagents 748 chlorination of alkanes 859 selenols, by reaction of Grignard reaction 1133 E/Z, enolate anions 1174 diselenides 1593 SEAr reactions 628 facial, for reactions at carbonyls with alkenes 924 probes 253 1088 with alkynes 924 process, and radicals 253 halogenation, of alkenes 858 selenones, from selenides 1507 shape, and guest–host interactions homogeneous catalysts in from selenides 1508 122 hydrogenation 1515 selenophosphoramide catalyst Shapiro reaction 1308 hydrocyanation 1211 1025 and deuterium labeling 1309 hydrogenation of alkynes 1516 selenosilanes, with epoxides 497 and isotope labeling 1309 ketones, with organometallics selenoxides, from selenides 1507 and organolithium reagents 1138 thermal elimination to alkenes 1308 of nitrenes 715 or alkynes 1311 mechanism 1309 of radicals 854 selenyl halides, and radicals 863 Sharpless asymmetric pinacol coupling 1595 self-condensation, and Claisen aminohydroxylation relationship 626 condensation 1253 1019–1020 sodium borohydride 1534 self-consistent field theory (SCF) Sharpless asymmetric syn, pinacol coupling 1595 36 dihydroxylation 1008 torquoselectivity 1390 self-immolative reagents 164 mechanism 1008 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2079

Sharpless asymmetric epoxidation [2,3]-sigmatropic rearrangement coupling with alcohols 547 1016 835, 1420 coupling with phosphates 547 and allylic alcohols 1017 and SeO2 oxidation 1482 Lewis acid catalyzed addition to mechanism 1017 and Sommelet-Hauser aldehydes 1148 Sharpless method, allylic rearrangement 835 with acetals 570 oxidation with selenium biocatalysts 1421 with aldehydes and transition dioxide 1482 enantioselectivity 1421 metals 1148 Shi epoxidation 1014 Mislow-Evans rearrangement with alkyl halides 545 Shibasaki catalysts 311 1422 silanes, and cleavage of ethers [1,5]-shift 1401 [3,3]-sigmatropic rearrangement, 540 homodienyl 1404 and amino Cope and conjugate reduction 1528 Shrock catalyst, for alkene rearrangement 1410 and formation of acylals 1105 metathesis 1427 and benzidine rearrangement and reduction of radicals 843 shuttle, molecular 130 1424 and the acyloin condensation Shvo’s catalyst 914 and Fischer indole synthesis 1598 and N-acylation 1250 1420 and the Brook rearrangement Si=Si double bonds 46 and the [i,j] nomenclature 1400 1437 side chain oxidation, aromatic and σ-bond migration 1400 silanes, arylation, and compounds 675, 1472 Claisen rearrangement 1414 Suzuki-Miyaura coupling side chains, on aromatic Cope rearrangement 1408 822 compounds, oxidation, of allyl vinyl ethers 1406 desilylation 1566 reactivity 1473 oxy-Cope 1409 halo, with enolate anions 721 side chain reactivity 1473 pericyclic 1415 halogenation of 862 structural limitations 1473 enantioselectivity 1418 hydroxylation 498 sigma bond overlap 94 [5,5]-sigmatropic rearrangement, ketones, deoxygenation 1578 sigma orbital overlap 92 and benzidine lithio, with aldehydes or sigma orbitals 5 rearrangement 1424 ketones 1191 [1,3]-sigmatropic alkyl migration sigmatropic rearrangement 1399 metal catalyzed, addition to 1405 antarafacial rearrangement alkenes 940 [1,5]-sigmatropic alkyl migration 1401 and hydrosilation of 1405 definition 1400 conjugated alkenes 1528 [1,2]-sigmatropic hydrogen shift of hydrogen, and ene arylation 822 1357 reactions 1401 coupling 545 [1,5]-sigmatropic hydrogen shift, suprafacial migration 1401 oxidation with Hydroperoxide homodienyl 1419 vinylcyclopropanes 1406 499 [1,5]-sigmatropic migration, of carbon migrations 1405 radical halogenation 862 carbon, orbital movement configuration of migrating reaction with hydroxide 239 1405 groups 1405 silanes, reduction of aldehydes or sigmatropic migrations, and diradical mechanism 1406 ketones 1540 configuration 1405 isotope labeling 1400 of aldehydes or ketones, metal sigmatropic migrations, of alkyl or [3s, 5s]-sigmatropic shift, catalysts 1540 aryl groups 1405 mechanism 1406 of carboxylic acids 1551 [1,2]-sigmatropic rearrangement sigmatropic shifts, and of carboxylic esters 1549 1406 cyclopropanes 1403 of conjugated alkenes 1528 [1,3]-sigmatropic rearrangement, sila-Baylis-Hillman reaction 1150 of imines 1553 HOMO 1401 sila-Pummerer rearrangement to hydrocarbons 1566 imaginary transition state 1603 silanes, trialkoxy, with aryl 1401 silanes, acyl, with Grignard halides 822 migration of hydrogen 1401 reagents 722 trialkyl, and acids, with alkenes of carbon, vinylcyclopropanes with RCu 722 1520 1406 silanes, alcohols, with alkenes vinyl 940–941 orbital overlap 1401 917 coupling with aryl halides photochemical, suprafacial aldehydes, deoxygenation 1578 822 1401 silanes, alkyl, radicals and with alkenes, metal catalyzed thermal 1402 hydrogen transfer 843 940 thermal, antarafacial 1401 with radicals 843 with aryl halides 1570 thermal, suprafacial 1401 silanes, allyl see allylsilanes metal catalyzed 822 [1,5]-sigmatropic rearrangement, coupling with alcohols 570 metal free 822 of alkyl 1406 coupling with amines 547 with fluoride ion 966 of hydrogen 1400 coupling with epoxides 547 with imines, enantioselectivity photochemical, antarafacial and the Sakurai reaction 966 1165–1166 1401 conjugate addition 966 with UV, reduction of thermal 1402 coupling 875 carboxylic acids 1551 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2080 SUBJECT INDEX

siletanes 498 silyl-Wittig reaction 1191 SN(ANRORC) mechanism, silica bound Cinchona alkaloids silylalkyl groups, neighboring Buchwald-Hartwig Cross 1008 groups 439 Coupling Reaction 787 silica gel 477 participation in solvolysis SN1 reaction see substitution addition of HCl to alkenes 910 439 SN1 reaction 410–418 and acetal cleavage 488 silylated carbocations 235 alkyl halides aqueous and ceric ammonium nitrate silylboranes, with alkynes 941 ethanolysis 378 631 silylcarbenes 269 amination of alkanes, and CrO3 oxidation 1448 silylcupration 962 mechanism 526 and dehydration of oximes to silylenes 1075 and adamantyl substrates 451 nitriles 1325 radical ions 265 and bridgehead carbons 413 and silicomolybdic acid 966 Simmons-Smith procedure, and and bridgehead carbons 691 and the Knoevenagel reaction carbenoids 1074 and carbocations 1351 1187 and diethylzinc 1075 and ether formation 491 as a dehydrating agent 1229 mechanism 1075 and hardness 410 heating aldoximines 1376 Simonini reaction 886 and ion pairs 414 sulfuric acid impregnated and the Hunsdiecker reaction and IUPAC system 411 1325 886 and leaving groups 1093 silicomolybdic acid, on silica mechanism 887 and nucleophiles 414 966 simultaneous addition 281 diazonium salts 771 silicon, and cis/trans isomers 12 simultaneous reactions 893 dihalides, gem-, from aldehydes and double bonds 12 single electron transfer (SET) see or ketones 1128 bond distance with carbon 24 SET of nucleophile 459 silicon tethered Pauson-Khand singlet oxygen formation of halogenation of alcohols 536 reaction 986 dioxetanes 1056 ion-molecule pairs 415 siloles 941 and autoxidation 869 ionization of a leaving group siloxanes, with aryllithium and calcium peroxide 411 reagents 822 diperoxohydrate 869 isotope effects 771 silver acetate, and decarboxylation and diradicals 870 kinetics 412, 771 684 and hydroperoxides 869 kinetics and concentration 771 silver carboxylates, and and photosensitization 869 mechanism, alcohols with acyl dihydroxylation of alkenes and photosensitizers 868 halides 1227 1007 and the ene reaction 952 and aryl diazonium salts silver catalyst 309 cycloaddition to dienes 1056 829 alkylborane coupling 883 cycloaddition with alkenes and carbocations 1336 silver compounds, and alkyl 1056 pseudo-first order 412 halides 471, 503 cycloaddition with rate determining step 410 silver cyanide 481, 600 phenanthrene 1056 solvent effects 410 silver nitrate, and alkyl halides Diels-Alder reaction 1056 SN1-like mechanism, reduction, 471 reagents for preparation 868 alkyl halides 1569 silver oxide, oxidation of benzylic with alkenes 868 SN1′ reaction see substitution, or allylic halides 1490 with alkenes, mechanism 870 SN1′ silver perchlorate, reaction with singlet, carbenes 266 SN1cA reaction 464 iodocyclopentane 76 methylene 271 halogenation of alcohols 536 silver, complex with ethylene 115 nitrenes 276, 1023 mechanisms 467–468 silyl alkenes, as a protecting group nitrenium ions 278 SN1cB reaction, mechanisms 527 877 radicals 261 SN1v, rate determining step 410 silyl enol ethers 579–580, 1181 singlets, and photochemistry 316, SN2 reaction see substitution See also enol silyl ethers 323–324 SN2 reaction, ab initio study 409 from aldehydes 721 singly occupied molecular orbital alkyl halides ethanolysis 377 Mukaiyama aldol reaction 1181 see SOMO alkylation of enolate anions with anhydrides 1253 sinister, and stereogenic centers 578 with imines 1182 186 and crossover experiments 407 silyl epoxides 547 sludge catalysts 1353 and ester formation 499 silyl ethers 492 small ring compounds, table and Hofmann-Martius reaction silyl ketene acetals 586, 1180 211–246 680 with imines 1182 SmI2, and catalysis 311 and leaving groups 1093 silyl substituents, and Smiles rearrangement 837 and organocuprates 556 conformation 198 and sulfenic acids 838 and propargyl systems 453 silyl thiols 923 and disulfides 838 and rate of exchange 407 addition to alkenes 922 and Truce-Smiles and rate of inversion 407 silyl-benzoin reaction 1216 rearrangement 838 and solvolysis 414 silyl-Heck reaction 814 SN′ reaction see substitution, SN′ and vinyl halides 449 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2081

and Williamson ether synthesis sodium amide, and the Haller sodium, alkyls 244 490 Bauer reaction 759 with ethers 1301 aqueous solution, free energy as a base 576 sodium, amalgam, and profile 408 sodium ammonium tartrate 170 Gomberg-Bachmann at atoms other than carbon sodium azide, and potassium pinacol synthesis 1593 409 iodide 1002 and decyanation 760 borderline 418 sodium bis(2- and formation of acyloins 1598 cation–molecule pair 418 methoxyethoxy)aluminum and formation of radical ions character, of the transition state hydride see Red-Al 1525 481 sodium bisulfite, reaction with and potassium 1599 complexes, ion–dipole 409 aldehydes or ketones 1111 and reductive coupling of esters cyanide with alkyl halides 599 sodium borohydride, and 1598 formation of aziridines 519 decyanation 760 and Wurtz-Fittig reaction 549 gas phase 406 and nickel, hydrogenation 1513 aryls 244 gas phase, free energy profile and oxymercuration 913 coupling of alkyl halides 549 408 and reduction of aldehydes and sodium, in ammonia, and Birch halogenation of alcohols 536 ketones 1533 reduction 1524 intramolecular 492 and reduction of alkynes 1522 and radicals 760 intrinsic barriers ad strain selectivity 1534 reduction of alkynes 1522 energy 424 sodium bromite, with amines 763 reduction of allenes 1522 ion pair destruction 417 sodium carbonate, base 514 reduction of aromatic ion pair formation 417 sodium cation, from sodium 1525 compounds 1524 mechanism, alcohols with acyl sodium chloride, electrolytic sodium, in ethanol, and reduction halides 1226 halogenation 708 of aldehydes or ketones and Grignard reagents and inorganic host 124 1537 alkyl halides 554 sodium hydroxide, and the and reduction of imines 1553 Friedel-Crafts alkylation Cannizzaro reaction 1601 reduction of carbonyls, 652 sodium hypochlorite see mechanism 1537 Menshutkin reaction 408 hypochlorites sodium, metal, and acyloin solvent effects 409 and epoxidation of alkenes condensation 1599 versus E2 reactions 1281 1017 and the Bamford-Stevens SN2′ reaction see substitution, and Jacobsen-Katsuki reaction 1309 SN2′ epoxidation 1017 surface area and reactivity 1599 SN2′ reaction, controversy 443 sodium ions, and crown ethers sodium, Wurtz coupling 549 coupling, palladium catalyzed 120 soft acids, and covalent bonds 360 565 sodium nitrate, and epoxides 523 and HSAB principle 361 stereochemistry 443 sodium nitrite see nitrite definition 359 vinylic epoxides 574 sodium nitrite with acid 761 soft and hard acids, table 360 and Grignard reagents 551 preparation of carboxylic acids soft bases, and covalent bonds and higher order cuprates 557 604 360 organocuprates 555–557 with alkenes, formation of soft bases, definition 359 SN2cA reaction 464 alkynes 1314 softness 359 mechanisms 468 sodium perborate, and and Lewis acids 359 of alcohols 536 hydroxylation of aromatic solid phase, and Grignard SNAr reaction, and transition compounds 674 reactions 1129 metals 777 sodium peroxide, and synthesis 1244 fluorination 792 hydroperoxide formation solid radicals 256 isotope effects 770 503 solid state, carboxylic acids, with mechanism 608, 768 sodium persulfate, and alcohols 1229 Buchwald-Hartwig Cross dimerization of conformations 220 Coupling Reaction 787 carboxylate salts 885 hydrogen bonds 109 Sneen formulation 418 sodium phenoxides, with carbon pinacol rearrangement 1354 Sneen’s ion-pair mechanism, dioxide 668 reactions 499 nucleophilic substitution sodium rubidium tartrate 148 solid-phase Fischer indole 696 sodium sulfhydride see synthesis 1419 SNi reaction, and nucleofuges 443 sulfhydride solid-supported chloroformates 440 sodium sulfite, with osmate esters cyclotrimerizations 1077 halogenation of alcohols 536 1006 solubility, and cyclodextrins 126 intimate ion pairs 440 sodium tetracarbonylferrate and hydrogen bonding 110 SNi’ reaction see substitution, (Collman’s reagent) 602 differential 166 SNi’ carbonylation of alkyl halides solvated electrons 775 SNi’ reaction, chlorination 443 604 solvating agent, chiral, for NMR SNN reaction see substitution, SNi with alkyl halides 602 175 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2082 SUBJECT INDEX

solvating power, Y, table 473 catalytic hydrogenation 1516 solvents see ionic liquids solvation, and anomeric effect Cope elimination 1307 achiral, CD of chiral molecules 201 decarboxylation 755 157 and cryptands 461 Diels-Alder reactions 1038 acidic 353 and nucleophilicity 460 E1cB mechanism 1282, 1284 acidic hydrogens 1171 and organolithium reagents 247 elimination 1286, 1294 acidity 352 and rate of reaction 461 enolate alkylation 576 and free energy 354 carbanions 242 enolate condensations 582 and acid strength 341–345 counterions 461 Gabriel synthesis 530 and acid–base reactions 576 energy, and Baker-Nathan heteroatom Diels-Alder and acidity 372 effect 93 reaction 1052 and base strength 349 Grignard reagents 245 Hofmann elimination 1306 and bond energy 32 of radicals 843 hydride reductions 1533 and carbenes 272 rule 470 keto-enol tautomerism 701 and cleavage of ketones 758 rule, for SN1 reactions and SN2 organocuprates 961 and Grignard preparation 748 reactions 470 rate of ionization of sulfonate and Grignard reagents 246, rule, SN2 reactions 470 esters 471 747 solvent acidity, and activity of reduction of alkyl halides 1567 and Hammett acidity function proton 352 SN1 reactions 410 352 and Bunnett-Olsen equation SN2 reactions 409, 470 and Lewis acid acidity 372 354 SRN1 reactions 776 and nucleophilic assistance 472 and dielectric constant 353 Suzuki-Miyaura coupling 799 and nucleophilicity 460, 471 and equilibrium constant 354 thiols with aryl halides 783 and proton transfer 351 and lyonium ions 353 solvent free, acylation of amines and rate of reaction 471 and pH 352 1239 and sonochemistry 332 solvent cages, and radical ions aldehydes with TMSCN 1210 and the Reformatsky reaction 421 aldol condensation 1178 1152 and radicals 554 alkenes, by decarboxylation of aprotic 469 and rearrangement of esters 1304 and hydrogen bonding 110 N-nitroaniline 677 alkyne anions, with aldehydes aromatic, complex formation and the Wittig rearrangement and ketones 1144 and radicals, reactivity 1384 amines, with epoxides 522 856 in the Stevens rearrangement oxidation to amides 1488 asymmetric, and synthesis 165 1382 and hypervalent iodine basic 353 radicals 751 oxidation of alcohols 1454 chiral, and NMR 174 solvent effects, and acidity 371 and microwave irradiation, PPh3 deep eutectic 395 and ambident nucleophiles 481 and I2 538 dielectric screening effects 469 and basicity 371 and the Beckmann dimethyl-2-imidazolidinone and bond energy 31 rearrangement 1376 1164 and carbenes 271 aromatic iodination 646 DME 1188 and carboxylic ester formation Baeyer-Villiger rearrangement solvents, effects, and free energy 499 1379 471 and charged nucleophiles 470 cyclopropylcarbinyl ion pairs 225 and conformations 193 rearrangement 1358 radicals, and reactivity 856 and elimination 1278 Dieckmann condensation 1254 solvents, enolate condensations and gauche conformations 192 Friedel-Crafts acylation 659 580 and Grunwald-Winstein Grignard reagents with allylic ether, and Grignard reagents equation 471–472 halides 1129 245 and Lewis acids 371 Henry reaction 1185 ether, and hydroboration 933 and limiting SN1 reactions 410 Knoevenagel reaction 1187 for the Heck reaction 811 and organolithium reagents 750 nitriles, from oximes 1325 free Passerini reaction 1265 and rate of reactions 470 oxidation, of alcohols 1448 green 393 and reactions 1288 of thiols to disulfides 1510 Grignard reagents 747 and SE1 reactions 692 reactions 395 hydrogen bonding 107 and SE2 reactions 696 and protection–deprotection in cyanide-alkyl halide and SN2 reactions 409 395 reactions 600 and SNAr reactions 770 sulfur ylid reaction 1205 induced chirality 157 and substitution reactions 471 TEMPO, oxidation of alcohols ionic 393 and syn elimination 1279 1452 ionizing power 472 solvent effects, aryl halides with thio-Michael addition 978 and leaving groups 472 sulfur nucleophiles 783 thiols with vinyl ethers 922 isotope effects 359 Bamford-Stevens reaction 1309 transamidation 1237 N-methylimidazole or bromine with alkenes 899 transesterification 1233 N-methylpyrrole 354 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2083

N-methylpyrrolidinone (NMP) and mechanism 415 SOMO–LUMO interactions, and 1117 and methyl group participation radical cyclization 974 nonpolar, and reactivity 390 438 SON2 mechanism, alkoxides with nucleophilicity, scale 472 and neighboring group aryl halides 783 phase-vanishing 1129 mechanisms 424 sonication see sonochemistry pinacol rearrangement 1354 and neighboring groups 425, Sonn-Muller¨ method, from polar and nonpolar 390 428, 430, 432 amides 1558 solvents, polar aprotic, and enolate and nonclassical carbocations sonochemistry 331–334 See also alkylation 576 427–428 cavitation and enolate condensations 580 solvolysis, and norbornyl systems and carbene formation 333 and ionic transition states 469 433 and carbohydrates 333 and phase transfer catalysis 474 and oxonium ions 419 and cavitation 331–332 and reactivity 390 and phenonium ions 432 and colloids 332 solvents, polarity 474 and picosecond absorption and Diels-Alder reaction and SN1 reactions 469 spectroscopy 416 333 and transition states 469 and racemization 416 and emission of light 332 solvents, protic 469 and rate enhancement 436 and gas vacuoles 331 protic verses aprotic, and SN2 and rate of ionization of and hot spots 332 reactions 470 solvents 472 and hydrostannation 333 solvents, radical complex 857 and rate of reaction 432 and metal carbonyls 333 rate of ionization, table 471 and rearrangement 438 and nucleophilic aromatic Reformatsky reaction 1152 and silylalkyl group substitution 333 separated ion pairs 417 participation 439 and organic solvents 332 sulfolane 1150 and SN2 reactions 414 and organolithium formation sulfur dioxide 412 and special salt effects 416 333 supercritical 2-propan-2-ol and stereochemistry 430, 433 and oxyallyl cation formation 1539 and structural effects 451 333 ammonia 393 and substitution 403 and sonoluminescence 332 carbon dioxide 392, 474, and sulfonate esters 419 sonochemistry, arylation reactions 876, 1542 and tosylates 416 333 UV of charge transfer complex and σ-bond participation 433 commercial instruments 333 473 solvolysis, benzoyl halides 125 cyclotrimerizations 1077 water 392 benzylic halides 455 imines, with organometallic with acidic hydrogens 1171 brosylates 427 reagents 1164 solvolysis 482 cyclopropanes 1398 origin of 331 alkyl halides, and carbocations of alcohols 378, 1342 power 333 306 of esters, and NMR 412 quasiadiabatic collapse 332 and mechanism 306 of iodocyclopentadiene 76 Reformatsky reaction 333 alkyl tosylates, rate of reaction of iodocyclopentane 76 reproducibility 333 452 of sulfonate esters 440 SRN1 reactions 333 anchimeric assistance 427 optically active compounds Weissler reaction 333 and alkene neighboring groups 433 Sonogashira coupling 308, 427 participation of hydrogen 439 816 and aromatic ring participation rates 379 and aromatization 1444 430 and azide ions 419 and cross coupling 818 and B strain 378 for alkyl bromides 450 and diazonium salts 818 and borderline mechanisms 419 of alkyl halides 379 and microwaves 335, 817–818 and brosylates 416 substituent effects on rate 428 and radicals 817 and carbocation stability 414 sulfonate esters 416, 426–427, in water 816 and carbocations 377 454 intramolecular 818 and cyclic groups 455 tosylates 426 metal catalyzed 978 and cyclobutyl compounds 436 table 433 preparation of macrocycles and cyclopropyl groups 455 Sommelet reaction, oxidation of 818 and cyclopropyl ring opening alkyl halides to aldehydes reaction conditions 816 stereochemistry 456 1490 sonoluminescence 332 and cyclopropylmethyl groups Sommelet rearrangement 1382 Source Index 1638 436 Sommelet-Hauser rearrangement Soxhlet extractor, and aldol and destabilizing groups 454 835, 1382 condensation 1173 and dioxane 419 and Hofmann elimination sp hybridization 11 and Grunwald-Winstein 835 sp orbitals 8 equation 452 and Stephens rearrangement sp2 hybrid orbitals 9 and I strain 379, 456 835, 1382 and hyperconjugation 94 and inversion 419 mechanism 835 sp3 hybrid orbitals 9, 15 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2084 SUBJECT INDEX

sparteine, and epoxides 1303 spin trapping, and carbenes 268 keto-enol equilibrium 701 and organolithium reagents 551 and radicals 252 keto-enol tautomerism 98 as chiral additive 960 spin traps 256 norbornyl carbocations 435 epoxides with organolithium and N-oxides 252 of arenium ions 611 reagents 1135 and NMR 253 table 612 with organolithium reagents chromotropic 252 of aromatic positional isomers 948 spin-conservation, Wigner rule 622 special salt effects, and solvolysis 323 of carbanions 237, 239 416 spiranes, and atropisomers 144 of carbocations 231, 233 Specialist Periodical Reports of and chirality 144 of dienes in Cope the Royal Society 1623 and enantiomers 144 rearrangement 1409 specific acid catalysis 355 spiro compounds 45 of enolate anions in solution specific rotation see enantiomers, spiro dioxides 1016 240 chiral compounds spiro[4.4]nonatetraene 46 of phenonium ions 432 specific rotation, and spiroborate esters 1539 of quinones 619 concentration 135 spirocycles, and the Nazarov of radicals 254–255, 299, 903, and enantiomeric excess 173 cyclization 958 1346 and enantiomers 136 spirocyclic compounds, from substituents effects 853 and molar rotation 136, 154 enynes 943 of π-complexes, table 612 and temperature 136 spirocyclic, β-lactams 1263 π-complexes 612 and wavelength of light 136, spirocycloxetanes, from radicals, and conjugation 256 155 Paterno-Buchi¨ reaction and steric hindrance 255 definition 135 1060 and substitution 255 spectra, Aldrich Library 1622 spirodienes 51 sulfenic acids 838 Sadtler Research Laboratories spirooxathianes, and tautomerism thermal, organocuprates 555 1621 103 stabilization, and delocalization spectral readings, kinetics 300 spiropentanes 1070 47 spectrophotometer, definition 314 spirotetraenes 45 of carbanions 242, 756 spectrophotometric measurements, splitting, and ESR 252 symmetrical 437 and solvent acidity 352 sponge, proton see proton sponge stabilizing groups, for carbanions spectroscopic analysis, radicals spontaneous dissociation 896 752 251 spontaneous reactions, and free stabilomers 1353 spectroscopy, and bond distance energy 283 stable carbenes 272 24 spontaneous resolution 171 stable radicals 258 and cyclic allenes 216 squalene 2,3-oxide, and steroids staggered conformations 189 and hydrogen bonding 109 944 stain, and radicals 853 and kinetics 300 squaric acid 56 starands 120 and rotational transitions 316 dianion and aromaticity 90 states, transition see transition deuterium quadrupole echo 123 pKa 90 states IUPAC classification 13 SRN1 reactions see substitution statistical effects, and acidity 366 of carbanions 240 SRN1 reactions, and SET 421 and acidity of diprotic acids photoelectron 12–15 diazonium leaving group 779 366 picosecond absorption 416 ferrous chloride catalysis 449 and dicarboxylic acids 366 spectrum, electromagnetic 316 Grignard reaction mechanisms stators, molecular 130 electronic 316 1134 Staudinger reaction 1263, 1565 spherands 119 mechanism 774 enantioselective 1059 spherical aromaticity 91 arylation, active methylene N-heterocyclic carbene catalyst spherical homoaromaticity 91 compounds 819–820 1058 sphericity 186 aryl amines from phenols sulfa- 1059 Sphingomonas pauchimobilis,and 790 thio- 1059 deracemization 172 and radical anions 775 steady state, and kinetics 299 and resolution 172 SRN2 reactions 776 steering wheel model 151–152 Sphingomonas sp. HXN-200 stability, alkynyl carbocations 448 Stephen reduction 1558 1486 and antiaromaticity 73 Stephens–Castro coupling 816 spin, and the Pauli principle 316 and aromaticity 71 and diazonium salts 818 electron 5 and hyperconjugation 94 and microwaves 817–818 spin conservation, and diradicals aryl diazonium salts 824 and radicals 817 1062 carbanion 238 metal catalyzed 817 spin delocalization 257 carbocations, and hydride shifts stereochemistry, alkenes 1289 spin forbidden transitions 316 1351 alkenes, from betaines 1200 spin inversion, and diradicals conformational see and bridged radicals 847 1062 conformation and catalytic hydrogenation spin states, and radicals 252 hemiacetals 1103 1519 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2085

and electrophilic addition 892 stereoelectronic control, and Friedel-Crafts alkylation 652 and electrophilic substitution hydrolysis 487 hydroformylation 990 688 tetrahedral mechanism 1092 of nitrenes 1023 and field effects 905 stereoelectronic effects, and Prins reaction 1213 and Friedel-Crafts alkylation radicals 853 radical hydrogen abstraction 652 stereogenic atoms see chiral 851 and mechanism 296 stereogenic atoms, absolute Stille coupling 718 and neighboring group configuration 148 Wagner-Meerwein shifts 1353 mechanisms 423 and diastereomers 158 stereoselectivity, Wittig-Horner and NMR analysis 155–156 and Fischer projections 148 reaction 1199 and ozonide formation and molar rotation 155 stereospecific synthesis 186–187 1468–1469 and monocyclic compounds stereospecificity, and E2 reactions and ozonolysis 1468–1469 179 1274 and SE1 reactions 691 and optical activity 138 [2+2]-cycloaddition reactions and solvolysis 430, 433 and pyramidal inversion 138 1066 and substitution at vinyl carbon and specific rotation 155 sulfonyl sulfur, nucleophilic 447 and symmetry 137–138 substitution, mechanism and the SE2 mechanism and the SN2 reaction 153 1266 688 Cahn-Ingold-Prelog system Wittig rearrangement 1384 and the SEi mechanism 688 149–152 steric acceleration, and the ene stereochemistry, borane chemical reactions 152 reaction 952 migrations 1386 creation of 147 steric congestion, and aromatics carbene with alkenes 1069 D/L nomenclature 148 57 carbocations 234 heteroatoms 138 steric crowding, and Dewar Cope rearrangement multiple centers 157 benzenes 60 1410–1411 NMR and absolute and pentahelicene 145 [2+2]-cycloaddition 1059 configuration 153 steric effects, and acidity 366 cyclohexanes 160 phosphorus 183 and ambident nucleophiles 481 cyclopropyl ring opening in quadrivalent 138 and basicity 366 solvolysis 456 R/S nomenclature 149–152 and bond energy 30 Diels-Alder reactions 1039 tervalent 138 and borane addition to alkenes E2 reactions 1291 stereogenic centers see 933 electrocyclic rearrangements stereogenic atom and catalytic hydrogenation 1390 stereogenic centers, and 1517 elimination 1290, 1296 glyceraldehyde 148 and Lewis acidity 367 epoxidation of alkenes 905, by reduction of prochiral and Lewis acids/bases 366 1206 ketones 1542 and radicals 256 halogenation of alkenes 994 stereoisomerism 133 and reactivity 377 halogenation, of alkynes 995 stereoisomers, allylic radicals and regioselectivity 481 hydroboration 905 256 and resonance 48 +I and -I effects 905 and cyclohexane derivatives and the Taft equation 388 in the Stevens rearrangement 198 base cleavage of ketones 758 1382 cyclohexane derivatives 180 electrophilic aromatic in the Stevens rearrangement diastereomers 158 substitution 625 1382 epimers 159 Lewis acids 367 ion pairs and internal return meso compounds 180 ortho substitution 416 out–in 181 rearrangement 1383 of alkyl migrating groups in oximes 1115 and cleavage of alkanes 759 sigmatropic migrations radicals 255 steric hindrance, and addition to 1405 relative configuration 159 alkenes 904 of migrating group, in topological, and catenanes 129 and alkene reactivity 902 rearrangements 1338, stereoretentive, alkene metathesis and arenium ion deprotonation 1340 1429 610 organocuprates with alkyl stereoselective Nazarov 958 and carbene addition to alkenes halides 555 stereoselective synthesis 161, 1070 organolithium reagents 750 186–187 See also synthesis and conformations 194 oxaphosphetanes 1197 enolate anions 584 [2+2]-cycloaddition reactions SN1 reactions at vinylic carbon stereoselectivity, aldol 1064 448 condensation 1175 and cyclobutadienes 74 SN2′ reactions 443 and 9-BBN 934 and dihydroxylation 1009 sulfur ylids 1206 carbocations 1352 and enol content 98–99 stereodifferentiation 1354 [3+2]-cycloaddition 1031 and high pressure 478 pinacol rearrangement 1354 free-radical addition 897 and hydride reductions 1534 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2086 SUBJECT INDEX

steric hindrance, and addition to Stille coupling 560, 717 and cyclobutane 209 alkenes (Continued) and alkynes 719 and cyclobutanes 208 and hydroboration 933 and ionic liquids 718 and cyclononyne 216 and hydrogen bonding 111 and microwaves 717 and cyclooctatetraenes 77 and mechanism 377 and supercritical carbon dioxide and cyclooctyne 216 and nucleophiles 461 718 and cyclopentyne 216 and propeller carbocations 233 carbonylative 719 and cyclopropene 215 and radical stability 255 formation of dienes 717 strain, and deformation of and reactivity of alkyl halides formation of enynes 719 aromatic rings 624 377 intramolecular 717 and dioxiranes 208 cis/trans isomers 178 mechanism 855 and E2 reactions 379 esterification of carboxylic SE2 (cyclic) mechanism 718 and epoxides 208 acids 378 stereoselectivity 718 and formal steric enthalpy 220 in nitriles, and the Ritter with alkynes 718 and fused ring aromatic reaction 1258 with borates 719 compounds 51 steric requirements, electrons 28 with boric acids 719 and geared molecules 219 steric strain see strain with enols 718 and hexahelicene 220 and substitution 450 with trifluoroborates 719 and homocubene 221 steroids 160, 380 with vinyl silanes 719 and lactams 213 and conformational STN Express 1633–1634 and leaving groups 465 transmission 380 Stobbe condensation 1183 and MO calculations 208 and dammaradienol 944 Stone-Wales rearrangement 1399 and molecular mechanics 204 and Johnson polyene stoppers, in rotaxanes 130 and nonbonded atoms 207 cyclization 944 molecular, fullerenes 131 and nonbonded interactions and rate of reaction 380 Stork enamine reaction 586, 1113 207 and remote dehydrogenation and hydrolysis of iminium ions and norbornene 217 1446 1098 and paracyclophanes 50 and the Barton reaction 1434 and N-alkylation 587 and PES 214 and the Stork-Eschenmoser enantioselectivity 587 and prismane 212 hypothesis 944 Stork-Eschenmoser hypothesis and propellanes 212 biosynthesis 944 944 and reactivity of radicals 853 derivatives, photochemistry Story synthesis 1332 and resonance 48 1402 strain energy 207 See also energy and ring size 214 elimination 1296 and fused ring aromatic and s character 208, 241 Stetter reaction 981 compounds 52 and semibullvalene 1413 and organometallics 1143 and molecular mechanics 207 and SN1 reactions 456 enantioselective 981 and SN2 intrinsic barriers 424 of alkyl halides 378 Stevens rearrangement 835, 1381, annulenes 79 and substituted aromatic 1422 A1,3 196, 1097 compounds 218 and CIDNP 1382 strain, and adamantanes 212 and tetrahedranes 212 and concerted mechanisms and addition to alkenes 379 and tricyclododecadiene 221 1382 and annelation 51 and unsaturated rings 214 and Hofmann elimination 1382 and azaadamantanone 213 and X-ray diffraction 213 and isotopic labeling 1381 and base cleavage of ketones strain, B, and rate of ionization and ring expansion 1381 758 378 and Sommelet-Hauser and bent benzene rings 220 and solvolysis of alkyl halides rearrangement 835, 1382 and benzocyclopropene 378 and sulfur ylids 1383 215–216 SN1 reactions, rate of reaction enantioselectivity 1382 and betweenanenes 216 451 isotopic labeling 1381 and bicyclic dienes 217 strain, Baeyer 207 mechanism 1381–1382 and bond distance 220 benzene derivatives 51 migratory aptitudes 1381 and Bredt’s rule 217 bicyclic alkenes 217 radical versus ion pairs 1382 and carbanion stability 241 cyclopropane 208 ring expansion of cyclic amines and carbocation formation 378 double bond 220 1381 and conformation 379 due to unavoidable crowding stereochemistry of the migration and crowded alkenes 220 218 group 1382 and cubane 211 strain, I, and acyl addition 380 suitable bases 1381 and cubene 221 and cyclic ketones 380 ylid formation 1382 and cyclic allenes 216 and reactivity 379 Stieglitz rearrangement 1378 and cycloalkanes 214 and solvolysis 379, 456 stilbenes 294 and cycloalkenes and strain, in ethylene oxide 208 photochemical conversion to cycloalkynes 216 in small rings 207 phenanthrenes 1398 and cyclobutadienes 74 intramolecular crowding 220 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2087

large angle 213 electron donating groups 454 substitution reactions, bimolecular large strain 215 electron withdrawing groups see substitution, SN2 medium rings 215 454 substitution reactions, bimolecular Pitzer 213 on rate of solvolysis 428 688 relief of, tetrahedral, rate SN1 reactions at vinylic carbon cine 772 constant 1091 452 compatibility, Pauson-Khand small angle 208, 215 SN2 reactions 450 reaction 986 small rings 215 thiols with alkynes 923 substitution reactions, compounds, table 210–211 β-andγ-substituents 454 electrophilic 281, 829 steric 206–221 substituents, and carbocations 234 substitution reactions, aromatic, and bond angles 206 and radical stability 255 activation hardness 625 and NMR 206 and β-substitution and and arenium ions 609 transannular 213–214, 379 γ-substitution reactions and neighboring groups 432 unavoidable 197 454 and phenonium ions 433 unsaturated rings 215 cyclohexane, energy 196–197 and the Hammett equation 626 strained cage molecules, strained, substitution reactions, acyl, and the Mills-Nixon effect 625 rearrangement 1431 nucleophilic 670 and π-complexes 611 strained imines 1023 and acylation 403 Brown σ* values 627 strained molecules, and bond and alkylation 403 Friedel-Crafts alkylation 648 angle 28 and allylic substrates 452 Hammett σ values 627 Strecker synthesis, and and benzylic substrates 452 hydrogen exchange 629 cyanohydrins 1211 and borderline mechanisms in fused rings 624 and radicals 1212 419 ipso attack 625 decarboxylative 1212 and β-branching 449 ipso position 633 enantioselective 1211 and carbenes 274 isomer distributions 625 organocatalysts 1211 and E1 reactions 1280 nitronium ions 633 structural variations 1211 and entropy of activation 422 orientation 614 structural effects, and solvolysis and HSAB 480 effect 622 451 and inversion of configuration partial rate factor 625 structural features, acyloin 689 rate 619 condensation 1598 and pressure 418 reactivity of substrates 626 structures, acid–base strength 361 and solvent effects 471 steric effects 625 and carbanions stability 242 and solvolysis 403 sulfur electrophiles 639 and concentration of Grignard and steric strain 450 substitution reactions, electrophilic reagents 246 and supercritical carbon dioxide unimolecular see and rate of H abstraction by 474 substitution, SE1 radicals 852 and the SET mechanism 452 addition–elimination and reactivity 375 and the Sneen formulation 418 mechanism 695 Grignard reagents 245 substitution reactions, aromatic, allylic substrates 694 Lewis see Lewis structures activating groups 776 and allylic carbanions 694 organolithium reagents 247 and aromaticity 71 and stereochemistry 688 organometallic compounds and enzymes 620 cyclic mechanisms 695 244–249 and metallocenes 66 double bond shifts 694 valence 227 and tropolones 65 substrate effects 695 strychnine, and resolution 167 annulenes 79–80 substitution reactions, first order sublimation, and resolution deactivating groups 776 reactions 412 170–171 halogenation 642 free radical 281 substituent effects, alkenes 899 ipso substitution 620 groups, table 457 allenes 904 of annulenes 83 IUPAC mechanism 465 and acidity 362 of azulene 68 IUPAC nomenclature 398 and field effects 454 rate of reaction 627 leaving groups, ability, table and Hammett σρ relationships substitution reactions, at acyl 468 455 carbon 452 and elimination 1294 and radicals 853 at bridgehead carbon 689 effects 464 and resonance effects 454 at mercury 690 nucleophilic 281 and SN1 reactions 451, 454 at neopentyl carbon 689 substitution reactions, nucleophilic and the tetrahedral mechanism at sulfur 716 aromatic 1285 455 isotopic labeling 1267 and Chapman rearrangement benzoic acid 363 SN2 mechanism 1267 1435 bromine, with alkenes 900 at vinyl carbon, and electron and leaving group order 779 Claisen rearrangement 1416 withdrawing groups 447 and Meisenheimer salts 769 dioxirane epoxidation 1014 and UV 446 and nucleophiles 779 electrocyclic ring opening 1389 and stereochemistry 447 and SN1 reactions 771 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2088 SUBJECT INDEX

substitution reactions, nucleophilic and ambident substrates 482 reactivity of groups, table 456 aromatic (Continued) and aryldiazonium salts 771 stereochemistry at vinylic and sonochemistry 333 and Baker-Nathan order 455 carbon 448 arynes, and substrate structure and bicyclic compounds 413 transition states 469 778 and carbocations 410, 413 with allylic rearrangement 441 benzyne mechanism 772 and conjugating substituents substitution reactions, SN1′ cine substitution 773 414 reactions 441 mechanism 768 and contact ion pairs 415 and ion pairs 441 nucleophile reactivity order and cubyl compounds 413 IUPAC nomenclature 441, 779 and diazonium salts 467 517 one-stage versus two-stage 776 and electrophilic addition 892 substitution reactions, SN1cA SNAr reactions 768 and electrophilicity 410 reactions 464 substitution reactions, and equilibria 414 substitution reactions, SN2 nucleophilic, and alkynyl and I strain 379 reactions (intermediate) carbon 452 and internal return 415 419 and aryl substrates 452 and intimate ion pairs 415 substitution reactions, SN2 and leaving groups 452 and ion pair mechanism 418 reactions, ab initio study and phase transfer catalysis 476 and ion pairs 415 408 and vinylic carbon 445, 452 and ionic strength 412 alkylation of carboxylate salts at sulfonyl sulfur 1266 and ionization 410 499 Grignard reagents 1266 and leaving groups 410 ambident substrates 482 isotope labeling 1266 and limiting SN1 reactions 411 and alcohol dehydration 495 mechanism 1266 and lithium perchlorate 471 and anchimeric assistance 422 SN2-mechanism 1266 and mixed SN2 reactions 418 and backside attack 404 stereospecificity 1266 and MO calculations 456 and Baker-Nathan order 455 at vinyl carbon, and the element and norbornyl compounds 414 and bicyclic compounds 456 effect 446 and nucleophiles 459 and bridgehead carbons 406, bimolecular see SN2 and partial retention 417 456 green 403 and pseudo first-order 412 and Brønsted plot 409 internal see substitution, SNi and racemization 414 and carboxylic esters 469 intramolecular 837 and rate of reaction 411, 450 and crossover experiments Sneen’s ion-pair mechanism and rearrangement 1338 407 696 and salt effects 470 and diol formation 1007 unimolecular see SN1 and SN2 reactions 412 and epoxides with with allylic substitution 441 and solvent polarity 469 organometallics 571 substitution reactions, polar and solvents 410 and free energy 409 nucleophilic aromatic 776 and special salt effects 416 and high-pressure mass radicals 844 and stereochemistry 416 spectrometry 406 rate of reaction 695 and strain 456 and hybridization 404 regioselectivity, with azo and substituent effects 451, and inversion 405 compounds 638 454–455 and ion pair mechanism 418 salt effects on rate 690 and tight ion pairs 415 and ion–dipole complexes 409 SE1 reactions 613 substitution reactions, SN1 and isotope effects 307 substitution reactions, SE2 reactions, at vinyl carbon and Marcus theory 292 reactions, and 447, 452 and mixed SN1 reactions 418 stereochemistry 688 alkynyl groups 448 and neighboring groups 422 SE2 reactions, mechanism 687 allene groups 448 and neopentyl systems 450 SE2′ reactions 688, 694 cyclopropyl groups 448 and nucleophiles 459 SE2Ar reactions, mechanism substituent effects 452 and nucleophilicity order 462 687 vinyl groups 448 and propellanes 456 secondary isotope effects 456 substitution reactions, SN1 and racemization 407 SEi’ reactions 694 reactions, carboxylate salt and rate of reaction 405, 450, and stereochemistry 688 alkylation 499 454 mechanism 687–688 kinetics and leaving groups 411 and retention 406 SN reactions, and bridgehead mechanism 410 and solvent effects 409 carbons 413 mechanism with alkyl halides and stereogenic atoms 153 SN’ reactions 443 378 and substituent effects 450 substitution reactions, SN1 mechanism, and ion pairs 414 and sulfonyl halides 504 reactions 410–418 nucleophilic aromatic 771 and the Hammond postulate alkyl halides in sulfur dioxide primary halides and metal ions 291 412 471 and transition state geometry and alcohol dehydration 495 rate of reaction, and B strain 452 and allylic substrates 452 451 and Walden inversion 405 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2089

substitution reactions, SN2 mechanism 774 sulfenes, intermediates 1267, reactions, chlorination of mechanism, and radicals 775 1313, 1418 malic acid 405 solvent effects 776 with diazo compounds 1208 Finkelstein reaction 534 substitution reactions, sulfonium sulfenic acids, and Smiles formation of alkyl halides 534 salts 453 rearrangement 838 gas phase 406 versus elimination reactions stability 838 intramolecular 407 1281 sulfenyl carbonyls 716 mechanism 404–409 leaving groups 1293 sulfenylation, carboxylic esters Menshutkin reaction 408 solvent effects 1295 716 protic versus aprotic solvents vicarious nucleophilic, of of ketones, lactams and 470 hydrogen 820 lactones 716 pseudo first-order kinetics 405 β-substituent and sulfhydride, sodium, with alkyl rate of reaction 450 γ-substituent effects halides 506 reactivity of groups, table 456 454 sulfide, dimethyl, as a leaving solvation rule 470 substrate compatibility, group 1490 solvent effects 470 organocuprates 963 sulfide, hydrogen see hydrogen solvolysis of benzylic halides substrate reactivity, acyl sulfide 455 substitution 1093 sulfides see thioethers synthetic reactions, table 457 substrates, ambident, allylic sulfides, and the Zinin reduction tight transition state 454 compounds 482 1559 transition state 407, 450, 469 and cyclic sulfates 482 aryl alkyl 508 substitution reactions, SN2 and SN1 reactions 482 by reduction of sulfones 1591 reactions, versus SN2′ aziridines 482 by reduction of sulfoxides, reactions 444 definition 481 reagents 1590 SN2′ reactions 442–443 epoxides 482 diaryl 508 and concerted reactions 443 SN2 reactions 482 formation of sulfines 1508 and cyclopropylcarbinyl substrates, and electrophilic from aldehydes or ketones halides 445 substitution 695 1110 and organocuprates 444 and SE1andSE2 reactions from diazonium salts 826 stereochemistry 443 695 from thiols 783 SN2cA reactions 464 definition 279 halo, Ramberg-Backlund-type¨ substitution reactions, SNAr reduction of ethers 1573 reaction 1317 reactions 776 variations, hydride reduction of hydroxy, from epoxides 496 activating ability of attached carbonyls 1533 of thioethers 508 groups 776 succinic esters, and Stobbe oxidation to sulfides or sulfones and ion–radical pairs 770 condensation 1183 1506 and Meisenheimer salts 769 succinimide, from NBS 864–865 oxidation to sulfones, metal and solvent effects 770 succinimidyl radical 865 catalysts 1506–1508 and π-complexes 770 sugars, aldehyde form 103 oxidation to sulfoxides 1507 dimer mechanism 770 and Kiliani-Fischer method tin, with alkyl halides 506 effect of substrate structure 776 1211 vinyl see vinyl sulfides Hammett relationships 777 and tautomerism 102 vinyl, from alkynes 923 mechanism 768 and the osazone test 1116 sulfinate salts, with organoboronic partitioning effects 770 suitanes 131 acids 511 rate of reactions 777 sulfa-Staudinger cycloaddition sulfinates, hydrolysis 485 substitution 776 1059 sulfines, from sulfides 1508 substitution reactions, SNi sulfamate esters 714 sulfinic acid salts, alkylation reactions, and retention of sulfates, alkyl, formation of ethers 511 configuration 441 494 and aryl iodides, preparation of IUPAC nomenclature 440 with alkoxides 494 aryl sulfones 784 mechanism 440 with halides ions 535 sulfinyl halides see halides substitution reactions, SNc with organolithium reagents sulfite, sodium, reduction of reactions 443 552 diazonium salts, and ion pairs 444 sulfates, and formation of mechanism 1566 substitution reactions, SRN1 aldehydes 913 sulfolane, and Baylis-Hillman reactions, and aryl halides cyclic, and ambident sulfates reaction 1150 774 482 solvent 1150 and nucleophilicity 779 from diols 482 sulfonamide salts, reaction with and potassium metal 775 leaving group 567 alkyl halides 530 and radical anions 775 with cyanide 600 with diaryliodonium salts and sonochemistry 333 sulfenes, from sulfonyl halides 530 and ultrasound 776 1208, 1314 sulfonamide-sulfonic acids, and vinylic halides 449 and amines 1267 co-catalysts 721 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2090 SUBJECT INDEX

sulfonamides, alkylation 527 and ylids 52 sulfonic acids, by oxidation of and the Hinsberg test 1269 antarafacial elimination of thiols 1505 arylation 590 sulfur dioxide 1317 autoxidation 1505 by reduction, of sulfonyl azides aryl, and the Smiles sulfonic acids, by reduction of 1565 rearrangement 837 sulfonyl halides 1270 of sulfonyl imines 1555 arylation 590 esters, hydrolysis 485 dealkylation, reagents 1592 by oxidation of sulfoxides 1505 reduction, to aromatic from sulfonamides 1241 by oxidation of thioethers 1505 compounds 1589 from sulfonyl halides and conversion to alkenes 1317 to disulfides 1590 ammonia or amines 1269 with organolithium reagents to thiols 1590 hydrolysis 1267 567 with halogenating agents 1269 hydroxy, by Knoevenagel sulfones, cyclic, cheletropic with imines 1264 reaction 1188 reactions 1317 with SOCl2 or PCl3 1270 N-arylation 529 conversion to cyclobutenes with sulfonamides, co-catalysts reagents for preparation 1269 1332 721 with alcohols 1268 with organolithium reagents sulfonium salts, and Swern with aldehydes 1122 1332 oxidation 1451 with alkenes or alkynes 930 sulfones, desulfurization, reagents substitution 453 with amines 1249 1588 sulfonyl acids, by hydrolysis of with anhydrides 1241 diaryl 641 sulfonic acid derivatives sulfonate esters, alkylation 589 extrusion of sulfur dioxide 1267 and solvolysis 419 1331 sulfonyl azides, with active as leaving groups 465 from alkyl halides 511 methylene compounds decomposition to alkenes 1305 from arylboronic acids 785 713 from alcohols 504 from Grignard reagents and sulfonyl chlorides, from from sulfonamides and alcohols sulfonyl halides 1270 organometallics and 1268 from organometallic reagents, sulfuryl chlorides 738 from sulfonyl halides and and sulfonyl halides 1270 with alkenes 642 alcohols 1268 and sulfonyl halides 1270 sulfonyl esters, hydrolysis 1267 hydrogenolysis 1575 from sulfides 1506 sulfonyl fluorides 641 leaving groups 466 metal catalysts 1506–1508 sulfonyl groups, as leaving groups migration 1367 from sulfinic acid salts 511 1267 rate of ionization, solvent from sulfonyl chlorides and stabilization of carbanions 241 effects 471 alkynes 999 sulfonyl halides see sulfonyl reagents for reduction 1575 from sulfonyl halides 511 sulfonyl halides, from diazonium solvolysis 416, 426–427, 440, and boronic acids 1271 salts 827 454 from sulfoxides 1507 reduction to sulfonamides 1555 with hydride reagents 1575 halo 999 sulfonyl sulfur, nucleophilic Friedel-Crafts alkylation 650 base induced elimination to substitution 1266 sulfonates, alkyl, with dienes 1317 Grignard reagents 1266 organolithium reagents conversion to epoxides 1206 isotope labeling 1266 552 pyrolysis to alkenes 1310 mechanism 1266 cyclic, from allylic sulfonate reduction 577 SN2-mechanism 1266 salts 921 reduction to sulfides 1591 stereospecificity 1266 from aryl sulfones 837 substitution via order of nucleophilicity 1267 from Smiles rearrangement 837 elimination–addition 449 sulfonyl-amino-alkenes, with leaving group 567 suprafacial elimination of sulfur NBS 1000 reduction, reagents 1572 dioxide 1317 sulfonylhydrazides, acyl, and vinyl, by sulfonic acid addition tetraions 1317 McFadden-Stevens to alkynes 921 vinyl 1000 reduction 1552 with cyanide 600 and the Michael reaction 959 base cleavage to aldehydes sulfonation, aromatic compounds with allenes 942 1552 639–640 with ketones 1188 sulfonylindoles 1025 and ionic liquids 641 sulfonic acids, addition to alkenes sulfoxides, allylic, and [2,3]-Wittig and microwaves 641 or alkynes 921 rearrangement 1422 sulfonation, with sulfur trioxide aryl, and sulfuric acid 685 and 1,4-elimination 1311 716 and the Jacobsen reaction sulfoxides, and atropisomers 143 sulfones 1333 685 and chirality 140 alkylation 589 conversion to phenols 781 and conformation 203 allylic vinyl, thio-Claisen sulfonic acids, by hydrolysis of and elimination 1297 rearrangement 1418 sulfonamides 1267 and resonance 52 and lack of chirality 138 of sulfonate esters 1267 and tetrahedral intermediates and resonance 52 of sulfonyl halides 1267 140 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2091

and ylids 52 and cyclopropanation, enzymatic reductions 1542 by oxidation of thioethers 1505 enantioselectivity 1207 epoxidation 1011 of thioethers, organocatalysts 1207 Glaser reaction 877 enantioselectivity and Michael ylids 1206 hydroamidation, of alkynes 1831–1832 chiral 1205 931 of thioethers, phase transfer phase transfer conditions 1205 hydroformylation, of alkenes 1508 sulfur, and aromatization 1443 989 catalytic hydrogenation 884 and carbanions stabilization oxidation of alcohols 1448 chiral 1419 243 Suzuki-Miyaura coupling 800 chiral, resolution 1507 and carbonylation of amines Oppenauer oxidation 1450 deoxygenation 1591 764 supercritical, ethane, isotope labeling 1591 and hydrogen bonds 111 Hydrogenation, aromatic desulfurization, reagents 1588 as a reducing agent 1591 compounds 1523 diaryl 641 inversion 140 supercritical, water, and the elimination, Hofmann’s rule and poison in catalytic Beckmann rearrangement Zaitsev’s rule 1310 hydrogenation 1513 1375 mechanism 1310 stabilization of carbanions 241 and the Heck reaction 811 from sulfides 1506–1507 stabilization of organolithium and the pinacol rearrangement halogenation, reagents for 709 reagents 248 1354 inversion 140 substitution, kinetics 1267 superelectrophilicity 410 oxidation to sulfones 1507 sulfonyl see sulfonyl sulfur superheating, and microwaves pyridyl 476 with diazo compounds 1208 334 pyrolysis to alkenes 1310 with diazonium salts 1208 superimposability, and chirality rearrangement to acetoxy with Grignard reagents 738 133, 138 sulfides 1603 with organometallics 738 and enantiomers 148 reduction 577 sulfuric acid, and arylsulfonic and optical activity 133 reduction to sulfides, reagents acids 685 superoxides, diketones 1466 1590 and nitric acid 632 potassium, with alkyl halides thermal elimination, and the Jacobsen reaction 685 503 mechanism 1311 and ylids 52 with alkyl halides or sulfonate treatment with anhydrides 1603 aromatic compounds 639 esters 503 with DAST 709 catalyst, for acetal formation superphane 88 with NBS 709 1103 supersonic molecular jet sulfoxonium compounds, for the Schmidt reaction spectroscopy, and pyrolysis to alkenes 1310 1373 conformations 188 sulfur carbanions 588 cleavage of ethers 486 supplementary information, sulfur compounds, and optical electronic structure 17 journals 1609 activity 140 fuming 641 supplements, of Beilstein 1618 sulfur dichloride, and with aromatic compounds suprafacial bond formation, chlorosulfenation 872 639 Diels-Alder reaction 1050 sulfur dioxide, and superacids 226 mono esters 504 suprafacial migration 1401–1402 and the reed reaction 872 sulfurization, reagents for 1109 in sigmatropic rearrangement as a guest 124 sulfuryl chlorides, with 1401 as a leaving group 1317, 1331 organometallics 738 suprafacial rearrangements, as solvent 412 with peroxides 853 configuration of migrating liquid 461 sultams, by [2+2]-cycloaddition groups 1405 with alkenes and halogen 872 1059 supramolecular catalysis 1206 sulfur electrophiles 639, 716 β 1264 supramolecular forms 131 sulfur hexafluoride, and electronic conversion to aziridines 1332 surfactants, cleavage of ethers structure 16 sultones, from alkenes and 540 sulfur monochloride, with alkynes sulfonate halides 921 Survey of Organic Synthesis 1629 1018 superacids see acids Suzuki coupling see sulfur nucleophiles 506, 1107 superbases see bases Suzuki-Miyaura coupling sulfur transfer reagents 1510 superaromatic 84 Suzuki coupling, alkyl–alkyl with potassium thiocyanate 508 supercritical, ammonia 393 coupling 801 sulfur trioxide, and sulfonation supercritical, carbon dioxide 474 and boronates, chiral 737 716 [3+2]-cycloaddition, with nitrile and microwaves 335 sulfonation of ketones 716 oxides 1032 with acyl halides 804 with trihalides to give acyl alkene metathesis 1429 Suzuki-Miyaura coupling 593, halides 484 and the Heck reaction 811 798 sulfur ylids 53 See also ylids aryl halides with amines 786 and arylation of silanes 822 and [2,3]-sigmatropic carbonylation of aryl halides and arylboronic acids 735 rearrangements 1421 821 and ball milling 800 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2092 SUBJECT INDEX

Suzuki-Miyaura coupling syn addition 892–893 reactions, table 458–459 (Continued) dihydroxylation of alkenes rotaxanes 128 and benzyne 803 1005 synthesis, stereoisomeric and metal catalysts 593–594 to alkenes 904 catenanes 130 and polymer-bound catalyst syn elimination 1277 synthesis, stereoselective 161, 801 syn nomenclature 161 186–187 compatible functional groups syn/anti dichotomy, and and active catalysts 165 801 elimination 1278 and active reagents 164 flow reactions 800 synchronous pericyclic transition and active solvents 165 functional groups 800 state 1037 and active substrates 162 in ionic liquids 800 synclinal conformation 190 and aldol condensation 166 in supercritical carbon dioxide synergistic effect, and chiral auxiliaries 164 800 cyclopropanation, alkenes and chiral circularly polarized intramolecular 799 1071 light 166 mechanism 802 synperiplanar, conformations and Cornforth model 163 metal catalyst 801 190–191 Cram’s rule 162 on alumina 800 synthesis, active substrate 161 and Felkin-Anh model 163 on alumina with microwaves and carbenes 272 and self-immolative reagents 800 and chiral pool 161 164 solvent effects 799 and crown ethers 119 and UV analysis 163 Swain-Lupton σ values 387 and dediazoniation 1587 asymmetric induction 165 Swain-Scott equation 461 and diastereoselectivity 162 double asymmetric synthesis and Marcus theory 462 and enol boranes 163 165 Swern oxidation 1490 and microwave chemistry 335 enantioselective reactions 165 and dehydration of amides to and reduction of aryldiazonium reduction of carbonyls 164 nitriles 1327 salts 1587 synthesis, stereospecific 186–187 and polymer bound sulfoxide and resolution 161 with alkene metathesis 1430 1451 and sulfonate ester leaving synthetic importance, alkene and sulfonium salts 1451 groups 466 metathesis 1428 of alcohols 1451 and supercritical carbon dioxide Synthetic Methods of Organic switches, molecular 128 392 Chemistry 1623 SYBYL 205 synthesis, asymmetric 154, sydnones, and aromaticity 89 161–166 T-shaped interactions 113 symbols, IUPAC nomenclature for and active catalysts 165 table, absolute hardness 361 mechanisms 399–400 and active reagents 164 absolute softness 361 symmetrical stabilization 437 and active solvents 165 acids and decarboxylation 753 symmetry, alternating axis 137 and active substrates 162 aldehydes, with carbanion and atropisomers 141–142 and aldol condensation 166 named reactions 1170 and biaryls 141–142 and chiral auxiliaries 164 alkene reactivity with Br2 and chiral compounds 134 and Cornforth model 163 899–900 and chirality 137, 146 and Cram’s rule 162 Beilstein, organization, table and circularly polarized light and Felkin-Anh model 163 1618 157 and self-immolative reagents Chemical Abstracts, collective and dipole moment 20 164 indexes 1617 and electronegativity 17 and UV analysis 163 current journals 1610–1612 and enantiomers 134 asymmetric induction 165 dipolar compounds 1029 and hydrogen bonds 109 chiral from achiral compounds electronegativity 18 and MO calculations 35 163 elimination and branching and monocyclic compounds double asymmetric synthesis 1293 180 165 field effects, +M and –M 376 and orbitals 6 enantioselective reactions 165 HSAB acids and bases 360 and stereogenic atoms 137–138 reduction of carbonyls 164 ionization of carboxylic acids axis, and chirality 136 with circularly polarized light 373 considerations, Diels-Alder 166 irregular serial publications reaction 1051 synthesis, Brook rearrangement 1624 forbidden transitions 316 1438 ketones, with carbanion named of orbitals in dienes 1391 by functional group type 1641 reactions 1170 perpendicular dissymmetric catenanes 128 M effects for groups 377 planes 141 double-asymmetric 935 NMR of carbocations 234 plane, and chirality 136 enantioselective, with nucleophilicity of reagents 462 and enantiomers 136 hydroboration 935 O and N compounds, bond symproportionation, addition of of pyrophosphate 122 angles 28 alkanes to alkenes 939 organic 118 of physical data 1621 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2093

oxidation number of functional and mass spectrometry 96 tellurides, diaryl, preparation 785 groups 1440 and nitrosomethane 102 preparation 510 rate of acetolysis 433 and oximes 101 tellurium salts, with rate of chlorination and and pH 97 hexamethyldisilazide nitration 612 and pyridones 101 1207 rate of ionization and solvents and quinazolines 103 tellurium ylids 1197, 1207 471 and rate determining state 304 tellurium, with Grignard reagents reactivity for SN2andSN2 and spirooxathianes 103 738 reactions 456 and sugars 102 telomers 897 reactivity, alkyl halides with and the Michael reaction 103 temperature effects, and amination ethanol 377 and the Ritter reaction 1257 of alkenes 924 review journals 1623 benzoxazine 103 elimination 1295 σ* values 385 decahydroquinazolines 103 temperature, and enantiomers 136 solvating power, Y 473 enol 327 and enthalpy and entropy 284 solvolysis of tosylates 433 imine-enamine 102 and hyperconjugation 306 stability of arenium ions 612 tautomerism, keto-enol 97, 701, and isotope effects 307 stability of π-complexes 612 915 and mechanism 303 substitution reactions, groups amides 99 and rate 303 457 and bond energy 98 and specific rotation 136 leaving group ability 468 and conjugation 98 dependence, reversal of synthesis reactions 458–459 and enol content 98 Friedel-Crafts alkylation thermodynamic values, and fluorine 99 681 carboxylic acids 373 and NMR 99 TEMPO (2,2,6,6- Tables of Experimental Dipole and solvent effects 100 tetramethylpiperidine-1- Moments 1621 and steric hindrance 98 oxyl free radical) 256, Tables of Interatomic Distances fusion type enols 98 1002 and Configurations in mechanism 97 and co-reagents used for Molecules and Ions 1621 tautomerism, nitro compounds oxidation of alcohols 1452 TADDOL based ligands 312 102 and formation of aryl nitriles Taft equation 383, 388 nitroso-oxime 101 673 Takai reaction 1203 of enols 753 and metal catalyzed oxidation of Tamao-Fleming oxidation 499, oxocarboxylic acids 103 alcohols 1452 941 phenol-keto 100 and the Diels-Alder reaction tandem, metathesis 1429 porphycenes 102 1054 Nazarov-Wagner-Meerwein porphyrins 102 catalyst, and aza-Michael sequence 958 proton-shift 100, 103 reaction 976 vicinal difunctionalization 961 ring-chain 102 metal catalysts, oxidation of tartaric acid, and enantiomers 135 theoretical calculations 100 alcohols 1452 diastereomers 158 valence 100, 1412 oxidation of alcohols, in ionic mechanism resolution 170 cycloheptatrienes- liquids 1452 and stereogenic centers 148 norcaradiene 1414 solvent free 1452 tartrate, diethyl, and Sharpless oxepin-benzene oxide 1414 to carboxylic acids 1492 asymmetric epoxidation tri-tert-butylcyclobutadiene stable radical 256 1017 1414 termolecular addition, mechanism epoxidation 1017 tautomerization see tautomerism 893 sodium ammonium 170 tautomers, and Cope termolecular processes 1222 taurine, catalyst 1506 rearrangement 1413 terpenes, reduction of nitriles to tautomeric effect 96 and hyperconjugation 96 methyl 1566 tautomeric forms, of bullvalene TBAT, aromatic fluorination 647 tert-butyl carbocations 230 1412 Tebbe reagent 1202 tert-butylcarbene 271 tautomerism 96–103 with aldehydes or ketones 1202 tert-butyllithium 245 form of nitro compounds 102 with lactones 1202 solvents and aggregation state alkylidene-2-oxazolidinone and titanium-carbenoids 1203 245 101 Techniques of Chemistry 1626 tervalent carbocations 698 allene–alcohols 444 Teflon, and microwave chemistry tervalent stereogenic atoms 138 amide-enol 1257 335 tetaalkylammonium and bromination of acetone 304 telluride, sodium, reduction of halochromates 1449 and carboxylic acids 103 nitro compounds 1585 [2.2]-tetrabenzoparacyclophane and enamines 102 with aryl nitro compounds 26 and hydration of alkynes 914 1600 tetrabutylammonium chloride, and hydrogen bonding 98 tellurides, aryl 818 catalyst, Grignard reaction and hydroxypyridine 101 alkyl 510 1132 and imines 102 coupling 805 tetrabutylammonium cyanide 601 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2094 SUBJECT INDEX

tetrabutylammonium hydroxide, tetrahydropyranosyls 201 and sulfur ylids 1205 thio-Michael addition 978 tetrahydropyrans, from alcohol conditions 721 tetrabutylammonium alkenes 918 thermodynamic, kinetic triphenyldifluorosilicate tetrahydropyridazines, by asymmetric amination of see TBAT Diels-Alder reaction 1054 alcohols 517 tetracarbonylferrate, sodium see tetrahydroquinolines 1403 reactions, free energy 290 sodium by cyclotrimerization 1078 stability, keto form 98 tetracarbonylferrate, and tetraions 1317 stability, of cations, allylic, Tischenko reaction 1602 tetrakis-triphenylphosphino- resonance 898 tetracyanomethylene, as acceptor palladium(0) 44 thermodynamically controlled 116 tetralones 660, 663 reactions 290 tetradehydro[38]annulene, tetramethylcyclooctatetraene thermolysis, alkanes and nitric bridged 83 146 acid 711 tetraenes, and homoconjugation tetramethylguanidinium cation of cyclobutenes 1389 45 based ionic liquids 393 of organoboranes 1368 tetraethyl lead 749 tetramethylisophthalamides 219 of trienes 1389 tetrafluoroborate anion, tetramethylpiperidine-1-oxy free of vinyl azides 1023 nucleophilicity 829 radical see TEMPO thexylborane 934 tetrahdyropyridines, via aza-Wittig tetramethylsilane 19 THF see tetrahydrofuran reaction 1202 tetramethytin, catalyzed THF, and Grignard reagents 247 tetrahedral intermediate 377, 450 methylation of and organolithium reagents 247 and I strain 379 aryldiazonium salts 830 complex with borane, with and reactivity 376 tetramine, macrocyclic 367 alkenes 933 and sulfoxides 140 tetrapropyl perruthenate see thia-Diels-Alder 1055 tetrahedral mechanism TPAP thia-Fries rearrangement 677 1088–1089 See also tetrasolvates, amide bases 369 thia-Michael see thio-Michael mechanism tetrasulfides 511 thia-Prins bicyclization 1215 in acid solution 1090 tetrazoles 1031 thiacarbenium ions 235 alcohols with acyl halides 1227 textbooks of organic chemistry, thiacrown ethers 118 and carbocations 1089–1090 graduate 1627 thiazoles, alkylation 591 and conformation 1092 undergraduate 1627 thiazolines, alkylation 591 and isotope labeling 1090 The Alkaloids 1626 thiazolium salts, and conjugate and leaving groups 1093 The Chemistry of Functional addition 979 and reaction rate 1090 Groups 1627 catalyst, benzoin condensation and the SET mechanism 1089 The Physico-chemical Constants 1216 directionality 1092 of Binary Systems in thiiranes 493 evidence for 1090 Concentrated Solutions alkenyl 1368 hydrogen in catalysts 1090 1621 and ionic liquids 509 isolation of intermediates 1091 the SET mechanism, and the and leaving groups 465 kinetics 1090 tetrahedral mechanism divinyl, Cope rearrangement position of equilibrium 1093 1089 1410 rate constant 1090 theory, Marcus 292 from alkenes 1018 reactivity 1089 thermal [2+2]-cycloaddition 1059 from alkynes, and sulfur relief of strain 1091 thermal effects, microwave monochloride 1018 reversibility 1094 chemistry 334 from diazo compounds and spectral detection of thermal extrusion of nitrogen sulfur 1208 intermediates 1092 1330 from epoxides 509, 1208 stereoelectronic control 1092 thermal hydro-dehalogenation, from halo disulfides 999 synthesis transformations 1094 aryl halides 1571 from thioketones and diazo type 1094 thermal stability, quaternary compounds 1208 tetrahedranes 1331 ammonium salts 476 and carbenes 1208 and strain 212 thermally allowed and forbidden reduction to alkenes 1532 tetrahydrobenzo-bis-cyclobutene reactions 1049 trans-thiiration 1018 624 thermochemical data, and with amines 523 tetrahydrofurans, conformation molecular mechanics 206 thio-Michael addition, and eutectic 203 thermodynamic acidity see acidity solvent 978 from alcohol-alkenes 918 thermodynamic conditions, aldol biocatalyzed 978 from allenes and alcohols 918 condensation 1179 metal catalyzed 978 halogenation of homoallylic enolate condensation 582 organocatalysts 978 alcohols 997 enolate reaction 582 thio esters, by hydration of tetrahydroisoquinolines, chiral, thermodynamic control, and alkynes 916 from carbonates 529 ambident nucleophiles from acyl halides and thiols Pictet-Spengler reaction 655 480 1227 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2095

thio-Claisen rearrangement thiocyanates, alkenes with enantioselectivity 1508 1418 isothiocyanates 1000 phase transfer 1508 thio-Michael addition 978 ammonium, and Mukaiyama oxidation, mechanism 1506 biocatalysts 978 reagent 533 poisons in catalytic enantioselective 978 and Hoesch reaction 672 hydrogenation 1513 eutectic solvents 978 and ultrasound 512 reagents for oxidation odorless 978 aryl 512 1505–1508 solvent free 978 from aryl halides 785 sulfide 508 tetrabutylammonium hydroxide by Katritzky vinyl, from thiols addition to 978 pyrylium–pyridinium alkynes 923 thio-Staudinger reaction 1059 method 512 with lithium naphthalenide 884 thio-Wittig reaction, and betaine, from alkyl halides 512 thioketones 1109 NMR 1197 from amines 512 conversion to thiolactams 1262 thioacetalization 1108 from ammonium thiocyanate Diels-Alder reactions 1053 reagents for 1108 533 from ketones 1109 thioacids, from carboxylic acids from aryl diazonium salts 785 from ketones, and hydrogen 1237 from diazonium salts 826 sulfide 1107 with alcohols 1237 from thiocyanate ion 512 from Lawesson’s reagent 1109 thioaldehydes see thioketones from thiophenols 512 stability, and trimerization thioaldehydes, conversion to heterocyclic 785 1108 thioamides 873 hydrolysis 1101 with carbenes 1208 from aldehydes 1109 thioesters, aldol-type with diazo compounds 1208 stability 1108–1109 condensation 1183 thiol acids, for acyl halides and thioalkyl ketones, from enolate conjugate addition 979 hydrogen sulfide 1237 anions 716 conversion to ketones 1158 thiol anions see mercaptides thioalkylation, and DCC 671 from thioamides 1235 thiol anions, as reducing agents of aromatic compounds 671 from thiocyanates 672 1588 of phenols 671 reduction to ethers 1580 thiol esters, from acyl halides and thioalkynes 508 reduction to thioethers 1580 thiols 1237 thioamides, alkylation 530 transesterification 1233 from ester 1237 and Caro’s acid 1111 with organometallics 1158 from thioacids 1237 and conformation 194 thioether-esters 1018 thiol-ene reaction, photoredox atropisomerism 177 thioethers, allylic, by [2,3]-Wittig 953 by hydrolysis of nitriles 1100 rearrangement 1421 β-thiolactams, from catalytic hydrogenation 884 from allylic sulfur ylids 1421 isothiocyanates 1264 conversion to thioesters 1235 vinyl, and thio-Claisen thiolactams, from lactams 1109 from aldehydes 1498 rearrangement 1418 from thioketones 1262 from amides 1238 thioethers, and DBU 507 thiolactones 1109 and microwaves 1109 and phase transfer 507 aminolysis 1247–1248 from chlorothioformates and and Williamson reaction 507 thiolate anions, for cleavage of amines 1269 by Stevens rearrangement of ethers 509 from isothiocyanates 669 sulfur ylids 1383 with aryl halides 783 from ketones 1604 carbanions, alkylation 578 thiolate ions, for demethylation from thioaldehydes 873 cleavage 884 509 torsional barrier 194 desulfurization 883 thiols, addition to alkenes 922 transamidation 1237 reagents 1588 addition to alkynes 923 via Beckmann rearrangement enantioenriched 508 addition to ketones 1107 1377 from addition of thiols to anions, reaction with vinyl with Grignard reagents 1159 alkenes 922 halides 446 thiobenzoates, reduction to from alcohols 507 aryl, from aryl halides 783 disulfides 1590 from alkyl halides 506–507 by addition of hydrogen sulfide thiocarbamates 765 from aryl diazonium salts and to alkenes 922 by hydrolysis of thiocyanates thiol anions 785 by reduction of disulfides, 1101 from thioesters 1580 reagents 1593 from isothiocyanates 1105 from thiols 506–507 catalytic hydrogenation 883 thiocarbonyl compounds, from from thioureas 508 conjugate addition 978–979 Lawesson’s reagent 1109 hydration of 916 conversion to thiosulfonates and bonding 12 lithio, and Peterson 1268 and E/Z nomenclature 177 alkenylation 1191 desulfurization 883 reagents for preparation 1109 oxidation, and ionic liquids reagents 1588 thiocarboxylic esters 1232 1506 from alcohols 506, 1305 thiocyanate ion, with alkyl halides oxidation, to sulfoxides or to from alkyl halides 506 512 sulfones 1505 from aryl diazonium salts 785 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2096 SUBJECT INDEX

thiols, addition to alkenes thiono esters, catalytic Tiffeneau-Demyanov ring (Continued) hydrogenation 884 expansion 1357 from diazonium salts 826 thionoesters, reduction to ethers tight ion pair 415 from hydrogen sulfide 506 1580 tight transition state 406 from isothiouronium salts 506 thionyl chloride 537 tin hydrides see hydrides from Lawesson’s reagent 506 and the SNi mechanism 441 tin sulfides, with alkyl halides 506 from organometallics 738 with alcohols 441 tin tetrachloride 368 from silyl thiols 506 with carboxylate anions 1236 Tishchenko reaction 1602 and alkenes 922 with carboxylic acids 1250 and aldol reaction 1602 from sodium sulfhydride 506 with sulfinic acids 1270 and hydroformylation 989 from sulfonic acids 1590 thiophenes, and aromaticity 62 catalysts 1602 from sulfonyl halides 1590 conversion to alkenes 1589 crossed 1602 from the Chugaev reaction desulfurization 884, Tishchenko-aldol transfer reaction 1305 1588–1589 1602 from thiourea 506 Friedel-Crafts acylation 659 titanium tetraisopropoxide, and thiols, oxidation of disulfides, and halogenation 645 Sharpless asymmetric microwaves 1509–1510 Paal-Knorr thiophene synthesis epoxidation 1016 thiols, oxidation to disulfides 1114 titanium-carbenoids, Tebbe 1505 reduction 1588 reagents 1203 mechanism 1510 resonance energy 63 titanium–salen complex, catalyst reagents 1509–1510 SEAr reactions 623 1017 reversible 1510 with nickel borohydride 884 titanium, catalyst 309 thiols, oxidation to sulfonic acids, thiophenols, conversion to and epoxidation 1017 autoxidation 1505 thiocyanates 512 diamination of alkenes 1021 thiols, poisons in catalytic from aryldiazonium salts 785 titanium, cyclopentadienide– hydrogenation 1513 with alkenes, anti-Markovnikov dimethylaluminum thiols, reaction with alcohols 508 addition 922 complex see Tebbe reaction with aziridines 526 with diaryliodonium 784 reagent reaction with carboxylates 508 thiophilic addition 1087 titanium, low valent 1321 silyl 923 thiophosgene, with amines and carbonyl coupling 1597 solvent free oxidation to 1240 titanocene dichloride, and disulfides 1510 with diols 1316 reduction of esters 1583 with acyl halides 1227, 1237 thiophosphates, from phosphine titanocene 1140 with alcohols and microwaves oxides 1268 dimethyl 1202 507 thiosulfate ion, with alkyl halides titanocene–zinc catalyst 311 with aldehydes or ketones 1108 511 TMEDA, and organolithium with alkenes 922, 1018 thiosulfonates, from thiols 1268 reagents 247–248 with alkyl halides 507 thioureas, and alkenes, metal tolanes see alkynes with alkynes 922–923 catalyzed formation of tolanes, by oxidative coupling of with alleneols 923 thiiranes 1018 dihalotoluenes 1508 with allenes 924 and inclusion compounds 123 Tollens’ condensation 1600 with aniline derivatives, flow chiral, catalysts 1125 and the crossed Cannizzaro reactions 784 conversion to carbodiimides reaction 1601 with aryliodonium salts 783 1260 Tollens’ reaction 1193 with boronic acids 784 formation of thioethers 508 and crossed Cannizzaro with carboxylic acids 1237 from addition of amines to CS2 reaction 1193 with diazonium salt, and Eosin 1127 and mixed aldol reaction 1193 Y catalyst 783 from isothiocyanates and toluene, dipole moment 19 with epoxides 496 amines 1125 toluenesulfonylmethyl isocyanide with hydrogen peroxide 1509 with alkyl halides 506 see ToSMIC with ketenes 923 third order reactions 297 tolylnapthalenes, and strain 220 with norbornene 1347 thiyl cation 993 topological, polarization 70 with phosphoric acid esters thiyl radicals 262, 890, 971 stereoisomers, and catenanes 1237 Thorpe reaction 1209 129 with vinyl ethers 922 intramolecular 1209 topology, hydrogen bonds 107 thionium ene cyclization 953 Thorpe-Ziegler reaction 1209 tormented aromatic compounds thionocarbonates, and the threads, molecular 128 51 Corey-Winter reaction three-center, cyclic transition state torquoselectivity 1390 1316 726 and Nazarov cyclization 958 cyclic, cleavage to alkenes hydrogen bond 108 torsional angle see angle 1316 threo nomenclature 160 torsional angle, and specific from diols and thiophosgene thujones 850 rotation 136 1316 Tiemann rearrangement 1372 energy diagram 191 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2097

torsional barrier, carbamates 194 transannular rearrangements 1345 aldol condensation 1176 of amides 194 transannular rearrangements, and amide hydrolysis 377 torsional diastereomers 143 alkyl groups 1345 and activation volume 390 torsional strain 139 transannular shifts, of hydrogen and calculations 37 and keto-enol tautomerism 702 atoms 1348 and free-energy 291 and molecular mechanics 204 transannular strain 214, 379 and H abstraction by radicals ToSMIC, and amination 520 See also strain 848 tosyl azides, with active methylene transesterification 505, 1232 and Hammet ρ-value 1287 compounds 712 and boiling point 1233 and high pressure 390, 478 tosylamines, halo 1000 and NHC 275 and intermediates 288 conversion to alkyl halides 543 and organocatalysts 1233 and proton transfer 356 from aziridines 525 and polymer bound siloxanes and solvent polarity 469 with epoxides 524 1233 and the Hammond postulate tosylates 465 See also sulfonate and superbases 1233 450 esters and vinyl acetate 1233 aryl migration 1347 acetyl, formation of carboxylic and Williamson ethers synthesis boat, Cope rearrangement 1410 esters 502 1234 carbocation, elimination 1297 alkyl, coupling 560 solvent free 1233 chair, Claisen rearrangement alkyl, rate of SN1 reactions 452 enzymatic 1233 1415 and solvolysis 416 Lewis acid catalysts 1233 chair, Cope rearrangement leaving groups 465 lipases 1233 1410 neopentyl, carbocation mechanism 1233 chelated 1176 formations 439 metal catalysts 1233 Claisen rearrangement 1415 propargyl, formation of allenes of lactones 1233 Cope rearrangement 1409 444 phase transfer catalysts 1233 cyclic, and Meerwein-Ponndorf- solvolysis 426 regioselectivity 1233 Verley reduction 1539 table 433 thioesters 1233 lead tetraacetate cleavage of tosylazides see azides transetherification 496 diols 1464 tosylaziridines, from epoxides and acetals 496 oxidative cleavage of diols 524 and enol ethers 496 1464 with alkenes 1023 and ortho esters 496 [2+2]-cyclizations, basis sets tosylcyanide see cyanides and oxocarbenium ions 496 1049 tosylcyanide 600 internal 496 [4+2]-cyclizations, basis sets tosylhydrazones see hydrazones transfer hydrogenation 1520 1049 tosylisocyanides, Knoevenagel amines, from nitro compounds transition states, dienes ring reaction 1188 1560 closure 1393 TPAP (tetrapropyl perruthenate), and nitrile reduction 1557 dipolar, and high pressure 478 oxidation of alcohols 1454 and organocatalysts 1528 E2 reactions 1287, 1291 catalytic oxidations 1454 and reduction of nitriles 1582 E2C reactions 1287 polymer-bound 1454 asymmetric reduction of imines elimination 1286 recovery of catalysts 1454 1554 epoxidation 1011 the Ley reagent 1454 diynes 1520 four-center, electrocyclic ring trans-cis isomers 180 metal catalyst 1520 opening 1391 trans-thiiration reaction 1018 reduction of conjugated alkenes geometry 291 transacetalization 1103 1527 and rate of SN2 reactions 452 transamidation 1237 reduction of imines, reagents imaginary, for [1,3]-sigmatropic and the zip reaction 1248 1554 rearrangement 1401 and thioamides 1237 reduction of ketimines 1554 ionic, and polar solvents 469 metal catalyzed 1237 transfer hydrosilation 940 lifetimes 291 polymer bound reagents 1238 transfer reaction, loose 406 solvent free 1237 Tishchenko-aldol 1602 Meerwein-Ponndorf-Verley transaminase, from Halomonas transformations, IUPAC reduction 1539 elongate 521 nomenclature 398 not detectable 291 transamination 520 transient grating spectroscopy, and pentacoordinate 404 and alcohol dehydrogenase 521 carbenes 271 planar, and E2 reactions 1277 enantioselective 521 transition energies 474 polarized 409 transannular hydride shift 1434 transition metals, and SNAr 777 pyrolysis of keto-ylids 1308 and isotope effects 1435 catalysts, and ether formation radical abstraction 845 transannular hydrogen atom shifts 491 radicals 853 1349 and selenides 510 SN2 character 481 transannular interactions 214 transition states 285, 287 SN2 reactions 407, 450 transannular ketone-ene reaction ab initio study, radical hydrogen substitution reactions 469 954 abstraction 849 syn elimination 1287 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2098 SUBJECT INDEX

transition states, dienes ring from alkyl azides and alkenes triflates, leaving groups 465 closure (Continued) 1022 vinyl 717 synchronous pericyclic 1037 photolysis 1022 with boronic acids 593 theory 285 thermolysis 1022 with trifluoroborates 595 three-center cyclic 726 triazolium precatalysts, acyloin triflic acid, ketones and alcohols tight 406 ester condensation 1598 584 and SN2 reactions 454 tributyltin dimer, and radical trifluoroacetic anhydride, and trigonal–bipyramidal 1266 cyclization 972 boranes 1387 transitional isomers, rotaxanes tributyltin hydride see hydride trifluoroborate salts, and 128 tributyltin hydride, and radical Friedel-Crafts alkylation transitions, in photochemistry see cyclization 969, 972, 974 653 photochemistry and radicals 263 trifluoroborates, alkenyl 595 transitions, in photochemistry 316 preparation 969 alkyl 595 transmetalation, and metallocenes reduction of radicals 972 alkyne coupling 878 744 tributyltin oxide, with vinyl alkynyl 568 and organocuprate formation halides 483 with aryl halides 819 744 tributyltin radical, from tributyltin amination 637 electromotive series 744 dimerization 972 and radical cyclization 975 of metal halides 744 tricarbonates, with amines 764 and Stille coupling 719 with metal halides 744 tricarbonylhydrocobalt 990 aryl 595 with metals 744 trications 229 conjugate addition 969 with organometallics 744 trichloroacetimidate, and the conjugate addition, metal transoid diene 1036 aza-Cope rearrangement catalyst 969 transposed, Paterno-Buchi¨ 1418 conversion to boronic acids 793 reaction, 2,4,6-trichlorobenzoyl chloride conversion to boronic esters photosensitization 1061 see Yamaguchi reagent 793 trapping intermediates 295 trichloroisocyanuric acid 763 coupling with aryl halides 804 tresylates 466 with carboxylic acids 1242 from boronic acids 738 leaving groups 465 trichlorosulfamate esters 1022 imines with boranes 1166 tri-sec-butylborohydride, lithium tricoordinated carbocations 232, oxidation to alcohols 1387 see Selectrides 234 oxidation with Oxone 1387 tri-sec-butylborohydride, tricyclododecadiene 220 vinyl, Heck reaction 815 potassium see Selectrides tricyclopropylcyclopropyl cation with alcohols 494 tri-tert-butylbenzene 218 240 with aldehydes, Pd catalyzed tri-tert-butylcyclobutadiene, and tricylcopentanoids 1081 1147 valence tautomerism 1414 triethylcarboxide, lithium 1386 with alkoxide 783 triacetoxy manganese, oxidation trienes, and cross conjugation with nitriles 1169 of allylic and benzylic 44–45 with triflates 595 alcohols 1450 and orbitals 44 5-trifluoromethyl, trialkoxysilanes, with aryl halides and the valence bond method dibenzothiophenium 822 45 trifluoromethanesulfonate trialkyltin hydride, reduction of by cheletropic reactions 1317 see Utemoto’s reagent alkyl halides 1568 conversion to cyclic alcohols trifluoroperoxyacetic acid 865 triaryl radicals 255 1385–1386 trifluorosulfonic anhydride 664 triarylamines, and chirality 146 from cyclic dienes 1389 trigonal hybridization 8 triarylbismuths, carbonylative from thiepin-1,1-dioxides 1317 trigonal–bipyramidal transition cross coupling 803 ring closure 1394 state 1266 triarylmethyl carbocations 233 thermal ring closure to cyclic trihalides, formation of esters 484 triarylmethyl radicals, chlorinated dienes 1389 from CCl4 and alkenes 484 257 triesters, from alkyl chloroformate hydrolysis of 484 triazenes, and azides 741 1253 trihomoaromatic 91 aryl 639 triethylamine, and Grignard trihomobarrelyl carbocations 234 aryl, rearrangement 679 reagents 247 triiodide cation, and aromatic from amines 762 triethylborane, and radicals 969 iodination 646 triazines, by trimerization of oxygen 970 triisopropylsilyl groups, and nitriles 1259 radical initiator 970 rotaxanes 130 triaziridines 139 triethyloxonium tetrafluoroborate, triketones, from diketone dianions triazoles, from alkynes and alkyl with alkynyltrialkylborates 1256 azides 1031 1389 trimerization, cyclic 735 from azides with alkynes 1033 triflates, and coupling 562 of aldehydes 1259 triazolines, by 1,3-dipolar addition with amines 785 of alkynes 1076 of alkyl azides 1022 with amines, and microwaves diynes 1077 extrusion of nitrogen 1330 786 intramolecular 1077 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2099

trimethylamine N-oxide 17 triple bonds, and delocalization twisted, acenes 85 trimethylenemethane, 39 amides 213 [3+2]-cycloaddition conjugated with p orbitals 42 formation of anhydrides 1034 triple metathesis 1429–1430 1235 radicals 260 triple-decker sandwiches 66 aromatic compounds 51 with alkenes 1034 triplet annulenes 71 carbocations 1343 trimethyloxonium triplet carbenes 266, 1068 compounds 214 tetrafluoroborate, persistent 268 Diels-Alder reaction 1050 conversion to methyl triplet nitrenes 276, 1023 double bonds 220 esters 1234 triplet nitrenium ions 278 twisting, and chirality 145 trimethylsilane, from silyl enol triplet oxygen, with alkenes 868 two-fold extrusion 1332 ethers 722 triplet radicals 261 trimethylsilyl amides, and nitrile triplet vinylnitrene 715 Udenfriend’s reagent, formation 1118 triplets, and photochemistry 316, hydroxylation of aromatic trimethylsilyl chloride, trapping 319, 323–324 compounds 865 acyloins 1599 triradicals 261 Ugi four-component reaction trimethylsilyl cyanide 1212, 1258 tris(trimethylsilyl)silane 970 1265 with alkyl halides 600 tritiation, aromatic compounds Ugi reaction 1265 trimethylsilyl halides, and acyloin 630 and imines 1265 condensation 1599 tritium, decay, for generation and peptide synthesis 1265 2-[(trimethylsilyl)methyl]-2- carbocations 449 isocyanide free 1265 propen-1-yl acetate 1034 hydrogen exchange 697 Ugi three-component reaction trimethylsilylacetamide, reaction isotope effects 305 1265 with ketones 721 labeling 448–449 Ullmann reaction 559, 797 trinitrobenzenes, and complex and diradicals, alternative catalysts 798 formation 116 rearrangements 1348 and electrochemistry 798 trioxane, from formaldehyde trityl carbocations 228 and microwaves 335 1259 triynes 89 enantioselective 798 trioxolanes, and ozonolysis 1467 triynes, cyclotrimerization 1077 heteroaryl halides 798 from aldehydes 1259 mechanism 1078 intramolecular 797 triphase catalysts 477 metal catalyzed 1078 regioselectivity 797 triphenylenes 61, 92 structural variations 1078 ultrasonic bath 477 and aromaticity 61 tropane 86 ultrasonic flow conditions, and and electron distribution 61 tropolones, and NMR 65 Barton reactions 755 solubility 61 and X-ray 65 ultrasonic waves, and acoustic triphenylmethide anion 242 aromatic character 65 cavitation 331 triphenylmethyl carbanion 239 bond alternation 65 and sonochemistry 331 triphenylmethyl carbocation 228, tropones 65 ultrasound 331–334, 599 234 and NMR 65 ultrasound see cavitation, dehydrogenation 1446 and X-ray 65 sonication, sonochemistry triphenylmethyl radical 254–255 aromatic character 65 ultrasound, acylation, of amines and IR spectra and UV spectra bond alternation 65 1240 255 pKa 65 alkylation and alkyl halides canonical forms 255 tropylium bromide 65 477 dimerization 255 tropylium carbocations 230 allylic compound oxidation stability 855 tropylium ion, and aromaticity 67 1479 triphenylphosphine oxide 1194 formation and stability 65 and acyl cyanides 1257 by oxidation of Truce-Smiles rearrangement 838 and aromatic halogenation 644 triphenylphosphine 1504 benzyne 838 and carbene generation 726 triphenylphosphine, and α-truxillic acid 136 and carbenoids 1074 tetracarbonylferrate 602 truxilic acid, and chirality 136 and cavitation 477 oxidation to triphenylphosphine Tsuji-Trost reaction 308, 564 and diazo compounds 868 oxide 1504 tub conformation, and dihydroxylation 1006 reduction of amine oxides 1586 cyclooctatetraene 146 and Knoevenagel condensation reduction of azoxy compounds tunneling control 291 333 1586 tunneling, E1-E2-E1cB spectrum and liquids 332 with carbon tetrachloride, and 1287 and lithium 552 carboxylic acids 1250 turnstiles, molecular 130 and nucleophilic substitution of triphenylphosphonium twist conformation 195 haloarenes 333 tetrafluoroborate, with azaannulenes 80 and permanganate oxidation of alkenes 928 annulenes 78 alcohols 1450 triphosgene, dehydrosulfurization twistane, and twist conformation and radicals 477 reagent 533 196 and reactivity 477 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2100 SUBJECT INDEX

ultrasound, acylation, of amines and choline chloride, deep and reactions 164 (Continued) eutectic solvent 497 and strained aromatic and reduction of nitro and Fischer-Hepp compounds 218 compounds 1559 rearrangement 678 and substitution at vinyl carbon and Reformatsky reaction 1152 and guest–host interactions 122 446 and SRN1 reactions 776 and Hoffmann rearrangement and triphenylmethyl radical and the acyloin condensation 1370 255 1598 and hydrogen peroxide 1016 and vibrational transitions 315 and the Baylis-Hillman reaction and resolution 167 and wavelength of maximum 1150 arylation 789 absorbance 315 and the Michael reaction 955 as a guest 123 and Woodward-Fieser rules and thiocyanates 512 as an inclusion compound 123 316 and zinc 1152 by carbonylation of amines 764 dienes 317 ultrasound, anhydrides from acyl catalyst, and nitrene insertion far 318, 901 halides with carboxylic 715 and photochemistry 314 acid salts 1235 complex 123 isotropic 154 aryl fluorides with amines 786 dehydration 1328 λmax 315 benzylic compound oxidation reagents 1328 light, alkenes with haloamines 1479 from addition of amines to 1000 Diels-Alder reaction, and carbon dioxide 1127 and electrocyclic ring azadienes 1054 from dicarboxylic esters, with opening 1389 ester hydrolysis 1220 urea 1249 and halogenation 863 Knoevenagel reaction 1187 from isocyanates and amines arylation of active methylene lactonization of alkenes 1026 1125 compounds 820 metals and pinacol coupling to carbodiimides 1328 paracyclophanes 50 1595 with acyl halides 1249 polyenes 317 oxidation of alcohols 1456 Wohler’s¨ synthesis 1126 spectra 114 Pauson-Khand reaction 986 ureates, catalyst 311 allylic benzenes 698 pulsed 332 urethanes, substituted see spectra-far, and alkenes 901 with Grignard reagents, metal carbamates substituted benzenes, table 318 catalyzed 1163 uronium salt, catalysts 1244 with silanes, reduction of with potassium permanganate, Utemoto’s reagent 948 carboxylic acids 1551 dihydroxylation 1006 UV (ultraviolet) 1621 ultraviolet see UV absorption peak 316 valence, and electronic structure umpolung 586 and addition of aldehydes to 16 and aldehydes 589 alkenes 981 multiple 7 and dithianes 589, 1110 and addition of sulfonyl halides of boron 8 N-heterocyclic carbene to alkenes 999 valence bond isomers 179 catalyzed Michael and annellation 61 valence bond method 4, 6 acceptors 957 and asymmetric synthesis 163 and trienes 45 unavoidable strain 197 and auxochromes 318 valence-bond Pauling resonance unconventional hydrogen bonds and conformations 188 energies, arynes 774 106 and cyclopropane 209 valence bond theory, and benzene undergraduate, textbooks of and detection of carbocations 37 organic chemistry 1627 413 valence electrons 15–16 ungerade orbitals 6 and electrocyclic reactions of valence isomers see isomers unimolecular substitution see stilbenes 1398 valence structures, types of substitution, SN1 and extinction coefficient 315 delocalization 227 universal NMR database, and and Fries rearrangement 676 valence tautomerism 100, 1412 absolute configuration 155 and halogenation of alkanes cycloheptatrienes-norcaradiene unshared electrons, and 857 1414 nucleophilicity 463 and halogenation of alkenes oxepin-benzene oxide 1414 unsolvated aryllithium reagents 995 tri-tert-butylcyclobutadiene 247 and hyperconjugation 92 1414 unstable cycloadducts, and methane 13 σ-valence, and field effects 385 [3+2]-cycloaddition 1031 and nitrosation 711 σ*-valence, and field effects 385 unsymmetrical biaryls 796 and nitrosyl halide 711 ρ-valence, and reactivity 382 unsymmetrical coupling 563 and photochemistry 314, 318 σ-valence, and reactivity 382 unsymmetrical pinacol coupling and pK 366 σ-values, and resonance and field 1594 and polyhalo addition to effects 386 upfield shifts 55, 57, 74 alkenes 1004 F and R values 387 ureas 124 and quinone substitution 446 Swain-Lupton 387 and cage structures 168 and radicals 254, 862 σ*-values, table 385 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2101

van der Waals forces 105 vinyl halides see halides, vinyl vinylogy 585, 1172 and guest–host interactions 123 vinyl halides, formation of vinyl and the E2 reactions 1277 and inclusion compounds 122 sulfides 507 definition 283 and molecular mechanics 204 vinyl iodonium salts, with sodium vinylphosphines 929 van der Waals radii, and Charton’s sulfonate 511 vinylsilanes see silanes ν values 388 vinyl radicals see radicals vinylsilanes, from vinyl iodide vanadium complexes 44 vinyl silanes see silanes 547 vapor form, of metals 748 vinyl silanes, and Stille coupling vinylsilanes, with aryl halides very fast reactions, kinetics 301 719 546 very weak acids 346 vinyl sulfides see sulfides vinyltin reagents 717 vibrational circular dichroism vinyl sulfides, alkylation 589 vinyltin, coupling with vinyl 154–155 from vinyl halides 507 triflates 717 vibrational levels, and from vinyl iodonium salts visible absorption peak 316 photochemistry 319 511 visible spectrum 154 vibrational transitions, and UV vinyl triflates, coupling with vitamin B2, organocatalyst 1506 315 organometallics 717 Vocabulary of Organic Chemistry vicarious nucleophilic substitution coupling with vinyltin reagents 1630 of hydrogen 820 717 volume, activation see activation Vilsmeier reaction, aliphatic 720 vinylation, N, of lactams 529 volume and haloacylation of alkenes vinylboranes see boranes volume of activation, and 1005 vinylboranes, from alkynylboranes E1-E2-E1cB Spectrum formation of keto-aldehydes and alkylating agents 1287 720 1388 and high pressure 478 Vilsmeier-Beckman reaction, vinylcycloalkanols 1404 von Braun reaction 544 formylation 664 vinylcyclobutanes, conversion to mechanism 544 Vilsmeier-Haack reaction 663 cyclohexenes 1407 nitriles, from amides 1327 reagents, photogeneration 1244 vinylcyclopropane rearrangement counterattack reagent 544 vinamidine proton sponges see 1406 von Richter reaction 779 proton sponge alkyne metathesis 1430 and mechanism 293, 295 vinamidine proton sponges 349 heteroatom 1407 von Richter rearrangement 834 vinamidine type bases 349 mechanism 1407 and labeling 834 vinyl acetate, and metal catalyzed 1407–1408 mechanism 834 transesterification 1233 vinylcyclopropanes 599 nitrogen leaving group 834 vinyl alcohols 99 from dienes 1432 VSEPR, nitrogen 13 vinyl aziridines, [1,5]-hydrogen sigmatropic rearrangement shifts 1403 1406 Wacker process 1499 vinyl boranes see boranes, alkenyl vinylidene carbene 1349 and Markovnikov’s rule 1499 vinyl boronates, with alkynes and vinylhalonium ions 230 aza- 1501 pinacolborane 936 vinylic carbon, addition– mechanism 1499–1500 vinyl carbanions, and elimination mechanism metal catalysts 1499 configurational stability 445 Wadsworth-Emmons see Horner- 244 and SN1 reactions 447 Wadsworth-Emmons vinyl carbenes 269 nucleophilic substitution 445 reaction vinyl carbocations see vinylic compounds, and SN1 1,3-Wagner-Meerwein carbocations reactions 452 rearrangements, and vinyl carbocations 231, 895 elimination–addition nonclassical carbocations vinyl carbons, retention of mechanism 448 1352 configuration 243 vinylic epoxides 573 Wagner-Meerwein vinyl chloride 185 vinylidene, gold 728 rearrangements 1350, orbitals 41 vinylidenecyclopropanes, 1352, 1377 vinyl compounds, and nucleophilic conversion to and alkanes 1353 substitution 452 alkylidenecyclobutanone and carbocations 1351 hydrolysis 485 1408 and Nametkin rearrangement vinyl cyanides see cyanides vinylnitrene, triplet 715 1352 vinyl cyanides, from vinyl vinylogous, aldol condensation and Nazarov cyclization 958 bromides 600 1178 and retropinacol rearrangement vinyl dihalides 997 Baylis-Hillman reaction 1445 1352 vinyl ethers, and radical conjugate addition 957 catalytic 1353 cyclization 975 Mannich reactions 1125 enantioselectivity 1353 dihydroxylation 1007 Michael reactions 957 mechanism 1353 hydrolysis 488 Mukaiyama aldol reaction 1181 migratory aptitudes 1341 vinyl groups, and Friedel-Crafts Nazarov 958 stereoselectivity 1353 alkylation 651 Wittig reaction 1197 Waits-Scheffer epoxidation 1015 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2102 SUBJECT INDEX

Walden inversion, and mechanism Web of Science 1614 in aqueous media 1194 296 weighting factor, and wave intramolecular 1201 SN2 reaction 405 equations 6 mechanism 1196 Wallach reaction 1121 Weinreb amides, acylation of betaines 1196 and the Leuckart reaction 1121 amines 1241 oxaphosphatanes 1196 with formamides 1121 and enolate anions 1174 phosphine variations 1194 Wallach rearrangement 1436, deprotonation 580 phospolane catalyzed 1199 1600 from carboxylic acids 1243 polymer-supported ylids 1195 and isotopic labeling 1436 reduction to aldehydes 1552 reaction partners 1201 and para rearrangement 1436 with Grignard reagents 1159 structural variations 1195 mechanism 1436 with hydride reagents 1552 thio-, and betaine 1197 photochemistry 1436 with organolithium reagents vinylogous 1197 warming, and microwaves 334 1159 with multiple bond substrates water, acyl addition 1095 intramolecular 1159 1195 to carbonyls 1095 with organometallic reagents Z-selectivity 1199 water, and alkyl, halides 483 1159 [2,3]-Wittig rearrangement 1421 and cage compounds 124 Weissler reaction, and and chirality transfer 1422 and hydrogen bonds 107 sonochemistry 333 and deformation of the and phase transfer catalysis 475 Wheland intermediates 608, 641 molecule 1421 and reactivity 391 Whitmore 1,2-shifts 1336 enantioselectivity 1422 and the Diels-Alder reaction Wigner spin-conservation rule structural requirements 1422 391 323 structural variations 1422 and the Sonogashira coupling, Wilkinson’s catalyst 43–44 Wittig Rearrangement 590, 1384, reaction conditions 816 and decarbonylation of 1422 angular 8 aldehydes 889 and ketyls 1384 basicity of amines 349 and enantioselectivity in and radicals 1384 bond angles 7 catalytic hydrogenation mechanism 1384 catalysts, for sulfonation of 1515 migratory aptitudes 1384 alkenes 922 and hydrogenation 1513 radical pair mechanism 1384 labeling 834 hydrogenation, mechanism stereospecificity 1384 pKa 1171 1518 with vinyl ethers 1384 promoted Michael reactions decarbonylation mechanism and Grignard reaction 1132 956 890 Wittig-Horner see Horner- removal as an azeotrope 1112 Willgerodt reaction 1604 Wadsworth-Emmons solvent, Buchwald-Hartwig and Claisen rearrangement reaction cross coupling reaction 1605 Wittig-Horner reaction, 787 Kindler modification 1604 stereoselectivity 1199 supercritical, pinacol mechanism 1605 Wittig, aza- see aza-Wittig rearrangement 1354 Willgerodt rearrangement 1350 Wittig, aza- 1202 with acyl halides 1218 Williamson ether synthesis 490 Wittig, boron- 1202 with alkynes and acid 915 and SN2 reactions 490 Wohl-Ziegler bromination 857, with amine halides 1367 and transesterification 1234 862 with aziridinium salts 1367 enantioselective 492 in ionic liquids 862 with azirines 1369 Williamson reaction, and epoxides Wohler’s¨ synthesis, urea 1126 with carbocations 1213 493 Wolf rearrangement 274, 1262, with isocyanates 1372–1373 and ionic liquids 491 1363 with isocyanides 1264 and microwaves 491 and Arndt-Eistert synthesis with ketenes 1364 and thioether formation 507 1364 wave equations 6 Wittig reactions 1193 and oxirenes 1365 and resonance 34 and amides 213 Arndt-Eistert synthesis 1364 wave function 3 and anti-Bredt alkenes 1196 conformation 1364 wave mechanical calculations 5 and arsine ylids 1197 flow reactions 1365 wave mechanics 3 and azaadamantanone 213 formation of ketones 1364 wavelength of light, and bond and epoxides 524 isotopic labeling 1365 energy 319 and microwaves 1196 mechanism 1364 and conjugation 317 and Peterson alkenylation photochemical 1364–1365 and microwaves 335 reaction 1191 Wolff-Kishner reduction 1577, and photochemistry 314 and photochemistry 1196 1584 and photolysis of dienes 1389 and Reformatsky reaction 1153 and semicarbazones 1577 and specific rotation 136, 155 and the Knoevenagel reaction carbanion intermediates 1578 wavelength of maximum 1188–1189 Huang-Minlon modification absorbance, and UV 315 E-selectivity 1199 1577 weak interactions 135 E/Z-selectivity 1199 mechanism 1578 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

SUBJECT INDEX 2103

Woodward-Fieser rules, and UV tropone and tropolone 65 acyl, pyrolysis to alkynes 316 tropones and tropolones 65 1308 Woodward-Hoffmann rules 1045, X-ray electron spectroscopy, and and [2+2]-cycloaddition 1063, 1082, 1297 nonclassical carbocations 1199 and cycloadditions 1080 435 and resonance 1194 and electrocyclic reactions X-ray photoelectron spectroscopy and the Wittig reaction 1194 1396 see ESCA from phosphonium salts and Woodward modification, of xanthate esters see esters base 1194 Prevost reaction 1007 xanthate esters, and the Chugaev reaction partners 1201 Wurtz coupling 554, 558, 747 reaction 1304 salt free 1194 organolithium reagents 750 pyrolysis 1304 suitable bases for formation Wurtz reaction 549, 798 xanthates, and elimination 1297 of ylids 1194 and Grignard reagents 880 bis-, conversion to alkenes with aldehydes or ketones and organolithium reagents 1315 1194 749 conversion to lactones 1026 ylids, planarity 53 formation of small rings 550 from alcohols and carbon polymer-supported, Wittig mechanism 549 disulfide 1107 reactions 1195 Wurtz-Fittig reaction 549 xanthine dye, photosensitizer selenium 53 intramolecular 549 1056 and formation of epoxides Wurtz-type coupling, Grignard xenon lamp, and photoirradiation 1205 reagent 1132 879 chiral 1205 organolithium reagent 1132 XtalFluor-E (and [Et2NSF2]BF4) 1,2-shift 1383 Wurtz-type reaction 1252 538 structural variations 1195 alcohols, with carboxylic acids sulfonium 1205 X-ray crystallography, 1230 sulfoxonium 1205 aminopyrenyl radical and formation of nitriles 1461 ylids, sulfur 53 257 and [2,3]-sigmatropic and annulenes 83, 86 Y-aromaticity 41 rearrangements 1421 and Bijvoet 149 Y, solvating power, table 473 and formation of cyclopropanes and bond distance 26 Yamaguchi protocol, and lactones 1205 and carbenes 272 1231 and Stevens rearrangement and conformations 188, 193 Yamaguchi reagent 1230 1383 and cyclobutadiene complexes ylides see ylids chiral 1205 74 ylids, and bonding 52 diastereoselectivity 1205 and D/L nomenclature 149 and field effects 241 epoxide formation, and diastereomers 159 and Hofmann elimination 1306 enantioselectivity 1205 and enolate anions 248 and orbitals 52 in ionic liquids 1206 and homoazulenes 80 and phosphonate esters 1198 kinetic versus thermodynamic and hydrogen bonds 108 and resonance 52 control 1205 and hyperconjugation 94 and sulfuric acid 52 mechanism 1205 and isopropyllithium 247 and the scoopy reaction 1200 polymer-supported 1205 and LDA 369 arsine 1197 reaction with epoxides 1205 and Meisenheimer salts 769 arsonium, with tosylimines solvent free 1205 and organolithium reagents 1208 sterochemistry 1206 247–248 carbonyl, [3+2]-cycloaddition with aldehydes or ketones and twisted alkenes 220 1030 1204 biphenylenes 51 dimerization 1201 with conjugated compounds cyclobutadienes 74 dimethyloxosulfonium 1206 intermediate of the Reformatsky methylid 1204 tellurium 1197, 1207 reaction 1153 dimethylsulfonium methylid with imines 1207 methyllithium 245 1204 with aldehydes or ketones 1193 nitroxyl radicals 257 functionalized 1207 with carbon dioxide 1201 of organolithium reagents 749 in the Steven’s rearrangement with electron-withdrawing of the methyl carbocation 224 1382 groups 1195 oxonium ion 235 intermediates 1307 ynamides, coupling amides and propellanes 212 nitrile, [3+2]-cycloaddition alkynes 529 Si-containing radical 258 1029 ynamines, alkylation 578 X-ray diffraction, and bond nitrogen 53, 835, 1202, 1382 hydration of 916 distance 23 and field effects 241 ynol ethers see ethers and Grignard reagents 245 phosphonate yids, and ynones, cleavage 1466 and paracyclophanes 50 conjugate esters 1201 with acyl halides 1156 and strain in medium rings 213 phosphorous and ketenes 1201 ytterbium catalyst, amines with pentalene derivatives 67 and the scoopy reaction 1201 oxetanes 525 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2104 SUBJECT INDEX

Z/E nomenclature, definition 176 and oxidation of and selenide formation 510 Zahlenwerte und Funktionen aus tetrahydropyranyl ethers and the Reformatsky reaction Physik, Chemie, 1459 1152 Astronomie, Geophysik, Knoevenagel reaction 1187 and ultrasound 1152 und Technik 1620 zeolite Y 231 in acid, and reduction of nitro Zaitsev orientation 1290 Ziegler alkylation 806 compounds 1559 Zaitsev’s rule 1288 Ziegler catalyst 942 with acyl chlorides 1227 and dehydration of alcohols zigzag acenes 85 Zinin reduction 1559 1299 Zimmerman-Traxler model 1176 reduction of sulfides 1559 and E1 reactions 1281 aldol condensation 1176 zip reaction 1248 and E2 reactions 1276 diastereoselectivity 1176 zirconium, and Schwartz’s reagent and Hofmann elimination 1306 zinc carbenoids 1074 938 dehydrohalogenation 1312 zinc chloride, and the Fischer zirconocene hydrochloride see elimination of boranes 1314 indole synthesis 1419 Schwartz’s reagent and alkenes 698 zinc reagents, aryl and heteroaryl Zn-Cu, carbonylation 604 and sulfoxide elimination 1310 561 zusammen, and alkene zeolites, and addition of thiols to zinc–amalgam and Wolff-Kishner nomenclature 176 alkenes 922 reduction 1577 zwitterion intermediates, and and carbocation formation 235 zinc, activated, and carbenoids elimination of hydroxy and conversion of aldehydes to 1074 acids 1323 nitriles 1117 and reduction of disulfides zwitterions, and amide formation and Meerwein-Ponndorf-Verley 1593 1249 reduction 1538 and Reformatsky reaction 1152 and ozonolysis 1467 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2105 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2106 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2107 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2108 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2109 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm

2110