JWST793-bind JWST793-Zweifel February 21, 2017 22:25 Printer Name: Trim: 279mm × 216mm



Index

A1,2-strain, 34, 216 alcohols in situ protection, 60, 95 A1,3-strain, 35, 41, 130, 145, 155, 186, 205 dehydration, 313 reduction, 86, 93 A values, in substituted cyclohexanes, oxidation, 42, 71 enantioselective, 104 27, 33 acyloins, 79 inthepresenceofketones,95 acetals to aldehydes and ketones, 71 synthesis, from in alcohol protection, 52 barium manganate, 77 acid chlorides, 87 in carbonyl group protection, 56 bismuth oxide, 79 alcohols, 73, 79 in diol protection, 55 ceric ammonium nitrate, 78 alkenes (via ozonolysis), 155 acetoacetic ester synthesis, 182 chemoselective oxidants, 76 alkynes, 165 acetonide, 55 Collins–Ratcliff reagent, 72 amides, 88, 210 acetylene zipper reaction, 348 Dess–Martin periodinane, 74 carbonylation, 257 acid-catalyzed benzylation, 49 Fetizon’s reagent, 77 Claisen rearrangement, 338

acidity, pKa values, 175–176 Jones reagent, 72 epoxy-ol rearrangement, 149 acyclic systems manganese dioxide, 76, 81 esters, 92, 103 allylic strain, 34 pyridinium chlorochromate, 73 glycol cleavage, 158 conformations, 21 pyridinium dichromate, 42, 73 nitriles, 88, 92 diastereofacial selectivity, 99 silver carbonate, 77 Alder, Kurt, 365 chelation-controlled addition sodium chlorite, 80 aldol reactions, 199 reactions, 102 sodium hypochlorite, 81 diastereoselective, 203 Cram’s rule, 101 Swern, 73 syn-anti selectivity, 206 double asymmetric induction, 100 TPAP (tetrapropylammonium enantioselective, 208 Felkin–Anh model, 101 perruthenate), 75 intermolecular, 199 hydroxyl-directed carbonyl TEMPO, 78 intramolecular, 200 reduction, 103 tertiary allylic alcohols, 79 mixed (crossed), 201 acyl anions, 6 triphenylcarbenium Claisen–Schmidt, 202 in Umpolung tetrafluoroborate,79 Mukaiyama, 202 cyanohydrin-derived, 10 propargylic, reduction of, 164 α−silyloxyketones in, 208 dithiane-derived, 7 protection, 48 Aliquat, 82 enol ether–derived, 11 stereochemical inversion, 98 alkenes lithium acetylide–derived, 11 synthesis, from allylic oxidation, 82 nitroalkane-derived, 9 alkenes, 125, 150 cleavage, 155 acylation, of COPYRIGHTEDallylic oxidation of alkenes, MATERIAL 82 dihydroxylation, 150 alcohols, 54 carbonyl reduction, 86, 93, 97 asymmetric, 152 amines, 46 carbonylation, 257 osmium tetroxide, 150 enolates, 181, 187, 191, 219 epoxide ring-opening, 140, 148, 245 potassium permanganate, 152 organocopper reagents, 244 aldehydes ruthenium trichloride, 159 acylium ion, 3, 265 conversion to amide, 75 dissolving metal reduction, 119 acyloin condensation, 355 deoxygenation, 61 epoxidation, 133, 144 acyloin oxidation, 79 diastereo- and enantiotopic faces, 99 diastereoselective, 145 N-acyloxazolidones, 209 as dienophiles in Diels–Alder directed, 144 acylsilanes, 272 reactions, 368 DMDO (dimethyldioxirane), AD-mix, 152 nucleophilic additions, 99, 244 137 Adam’s catalyst, 115 oxidation, 80 enantioselective, 146 AIBN, 61, 154, 317, 347 protection, 56 halohydrin approach, 138

Modern Organic Synthesis: An Introduction, Second Edition. George S. Zweifel, Michael H. Nantz and Peter Somfai. © 2017 John Wiley & Sons, Inc. Published 2017 by John Wiley & Sons, Inc. JWST793-bind JWST793-Zweifel February 21, 2017 22:25 Printer Name: Trim: 279mm × 216mm

 Index

alkenes (Continued) reduction to hydrocarbon, 90, amine-borane complex, 107, 186 hydrogen peroxide, 135–136 154 amine oxides, pyrolysis of, 316 Jacobsen, 150 alkyllithium reagents, 227, 232 Ando–Wittig reaction, 331 peroxy acids, 133 alkynes anomeric effect, 30 sharpless asymmetric, 146 alkylation, 345 anti-Bredt, 32 halolactonization, 153 carboalumination, 293, 321 anti-conformation of butane, 22 hydration, 125 carbocupration, 322 Appel reaction, 16 hydroboration–oxidation, 125 dissolving metal reduction, 164 Arbuzov reaction, 329 oxymercuration–demercuration, hydration, 165 aromatic compounds 131 hydride reduction, 164, 319 reduction, 121. See also Birch hydroboration, 125 hydroalumination, 293, 319 reduction asymmetric, 129 hydroboration, 162, 296 synthesis, 125, 230, 235 chemoselective, 128 hydrozirconation, 294 aryl esters, in carboxyl group protection, diastereoselective, 130 isomerization, 348 65 organoborane oxidation, 129 methylalumination, 321 aryllithium reagents, 230, 232 regiochemistry, 127 oxidation, 81 asymmetric induction, 86, 100 stereochemistry, 128 oxymercuration, 166 asymmetric reactions hydrogenation, 115 reduction via alkenylborane aldol, 209, 211 oxidation, 133, 144 protonolysis, 162 alkylation, 183, 198 lead tetraacetate, 159 semi-hydrogenation, 160 allylation, 261 Lemieux–Johnson, 157 synthesis, 343 allylic alkylation, 306 osmium tetroxide, 157 from aldehydes, 344, 349 allylic oxidation, 84 potassium permanganate, 158 alkynylide alkylation, 345 conjugate addition, 178, 247 ruthenium tetroxide, 159 allene isomerization, 349 cyclopropanation, 256 oxymercuration–demercuration, 131 Corey–Fuchs bromomethylenation, Diels–Alder, 373 ozonolysis, 155 344 dihydroxylation, 152 ruthenium tetroxide, 159 dehydrohalogenation, 343 epoxidation, 146, 150 stereochemical inversion, 142 enol phosphate elimination, 345 halolactonization, 155 synthesis, 39, 313 Fuchs alkynylation, 347 hydroboration, 129 from alkynes, 160, 318 Gilbert’s reagent, 349 hydrogenation, 118 amine oxide pyrolysis, 316 alkynylide anions, in alkyne synthesis, ketone reduction, 105 Chugaev reaction, 316 345 Mannich reaction, 214 Claisen rearrangement, 338 alkynylsilanes, 265 metalation, 234 Cope elimination, 316 allene isomerization, 349 Robinson annulation, 220 ß-elimination reactions, 39, 313 π-allyl-palladium, 304 Horner–Wadsworth–Emmons allyl vinyl ethers, 338, 343 Babler oxidation, 79 reaction, 329 allylic alcohols Baeyer, Adolf von, 135 Julia–Kocienski olefination, 335 epoxidation, 144 Baeyer–Villiger reaction, 135 Julia olefination, 334 enantioselective, 146 Baldwin’s rules, 193 McMurray reaction, 360 hydroxyl-directed, 144 Barbier reaction, 237, 254 metathesis, 375 oxidation of tert-allylic alcohols, 79 barium manganate, 77 from Pd-catalyzed coupling synthesis Barton, Derek H.R., 21 reactions, 285 oxidation of alkenes, 82 Barton–McCombie deoxygenation, 316 Peterson olefination, 332 reduction of propargylic alcohols, 9-BBN (9-borabicyclo[3.3.1]nonane), pyrolytic syn elimination reactions, 164 105, 127, 257, 298 316 resolution, 150 benzamides, 46 selenoxide elimination, 317 allylic metalation, 233 p-benzoquinone, 84, 250 Shapiro reaction, 336 allylic strain, 34 benzyl esters, 65 sulfoxide pyrolysis, 317 allylic substitution, palladium-catalyzed, benzyl ethers, 48 Wittig reaction, 324 304 N-benzylamine, in NH group protection, xanthate pyrolysis, 316 allylsilanes, 268 46 transposition, 338 Alpine-Borane, 105 benzylation, acid-catalyzed, 49 Wacker oxidation, 167 alternating polarity disconnections, 4 benzylic metalation, 233 alkenylboranes, 162 aluminum hydrides, 86 benzyloxycarbonyl (Cbz) group, 46 alkenyl halide synthesis, 288, 320 amides Bestmann reagent, 328 alkenyllithium reagents, 229 alkylation of amide enolates, 186 betaine, 142, 325 alkenylsilanes, 266 in NH group protection, 46 BHT, 65

alkyl halides pKa, 176 bicyclo[4.4.0]decane (decalin), 31 in organolithium reagent preparation, reduction, 88, 186 bicyclo[2.2.1]heptane, 32 229 Weinreb amide, 210 bicyclo[4.3.0]nonane (hydrindane), 30 JWST793-bind JWST793-Zweifel February 21, 2017 22:25 Printer Name: Trim: 279mm × 216mm

Index 

BINAL-H, 107 terminology, 85 bridged bicyclic systems, 32 BINAP, 118, 266 zinc borohydride, 89 chair, 24 Birch reduction, 121 carbonylation, 257 cyclohexyl systems with chiral quaternary carbon formation, carboxyl groups, protection of, 62 sp2-hybridized atoms, 33 124 carboxylic acids, destabilization energies, 27 1,3-cyclohexadiene formation, 123 enolate alkylation, 186 envelope, 24 cyclohexenone formation, 123 reduction using borane, 93, 96 of six-member heterocyclic systems, reaction conditions, 121 synthesis, from 29 regiochemistry, 122 alcohols, 73, 76, 80, 149 tricyclic systems, 33 bismuth oxide, 79 aldehydes, 80, 158 twist boat, 24 boat conformation, 24 alkynes, 81, 166 conjugate addition (1,4-addition) Boc (t-butoxycarbonyl), 47 enone oxidative cleavage, 159 of hydrides, 94, 191 bond dissociation energies, 264 Grignard reagents, 228, 237 Michael-type reactions, 178 borane-dimethyl sulfide, 125 periodate oxidative cleavage, 159, of organocopper reagents, 191, 245, borane-tetrahydrofuran, 125 209 247, 323, 372 borohydrides, 88 silyl enol ether ozonolysis, 157 of sodium benzenesulfinate, 335 boron enolates, 205 Carroll–Claisen rearrangement, 340 stereochemistry of, 39, 249 boronic ester homologation, 259 cascade reactions, 18 consonant patterns, 4 Brassard’s diene, 366 Castro-Stevens reaction, 302 convergent synthesis, 17 Bredt’s rule, 32 catecholborane, 296 coordination number, 285 Breslow intermediate, 358 Cation-π cyclizations, 361 cope elimination, 316 bromonium ion, 40, 153 CBS reduction, 106 Corey, E.J., 1 Brook rearrangement, 271, 272 Cbz, 46 Corey–Chaykovsky reaction, 139 Brown, Herbert C., 125 ceric ammonium nitrate, 49, 78 Corey–Fuchs bromomethylenation, 344 Brown2 gasimeter, 161 ceric chloride, 95, 159, 240, 332 Corey–Kim oxidation, 74 Burgess reagent, 315 cerium bromate, 78 Corey lactone, 154 Burgi–Dunitz¨ trajectory, 97 C–H activation, 84 Crabtree’s catalyst, 118 butane, 22 Chair conformation, 24 Cram’s rule, 101 t-butyl esters, 64 chelation control, 102, 203 cross conjugated system, 189 t-butyl ethers, 48 chemoselective reactions crotylboration, 261 t-butyl hydroperoxide (TBHP), 82, 137, epoxidation, 134 crotyllithium reagents, 233, 262 146 hydroboration, 128 Crown ether, 232, 331 t-butyl peroxybenzoate, 83 hydrogenation, 116, 161 cupric acetate, 79 t-butyldimethylsilyl (TBS) ethers, 51 oxidation, 76 Curtin-Hammett principle, 36 t-butyldiphenylsilyl (BPS) ethers, 52 reduction, 93 cyanidation, 258 B-chlorodiisopinocampheylborane cyanocuprate reagents, 242

Cadiot–Chodkiewicz reaction, 304 (Ipc2BCl), 106 cyanohydrins, 10, 81 camphorsulfonic acid (CSA), 56, 124, chloroiodomethane, 139 cyclization reactions, 193, 355 144, 149 chlorotris(triphenylphosphine)rhodium, in aldol condensations, 200 CAN (ceric ammonium nitrate), 49, 78, 117 Baldwin’s rules, 193 236 chromic acid oxidation, 72 cation-π, 361 carbamates, in NH group protection, chromic anhydride, 83 gold-mediated, 276 46 Chugaev reaction, 316 intramolecular free radical, 355 carbenium ion, 3 Claisen condensation, 179 acyloin condensation, 355 carbenoid, 139, 255 Claisen rearrangement, 338 McMurray reaction, 360 carboalumination, 293, 319, 321 asymmetric Claisen rearrangement, Pinacol coupling, 359 carbocupration, 322 342 pericyclic, 364 carbonyl groups Carroll–Claisen rearrangement, 340 Diels–Alder cycloaddition, 364 acetalization Eschenmoser variant, 341 1,3-dipolar cycloaddition, 375 with O,O-acetals, 55 Ireland variant, 341 ring-closing olefin metathesis, 375 with S,S-acetals, 60 Johnson ortho-ester variant, 340 cyclobutane, 23 polarity reversal (Umpolung), 6 Claisen–Schmidt reaction, 202 cyclohexanes reduction, 85 Clemmensen reduction, 62 conformations, 24 diisobutylaluminum hydride, 91 Collins-Ratcliff reagent, 72 destabilization energies, 27 lithium aluminum hydride, 86 computer-assisted molecular modeling, cyclohexanones, conformations, 33 lithium borohydride, 89 35 cyclohexenes, conformations, 34 lithium trialkylborohydride, 90 conformational analysis cyclopentadienone, 367 Rosemund procedure, 87 acyclic systems, 21 cyclopentane, 24 sodium borohydride, 88 anomeric effect, 30 cyclopropanation, 254, 276 sodium cyanoborohydride, 90 boat, 24 cyclopropane, 23 JWST793-bind JWST793-Zweifel February 21, 2017 22:25 Printer Name: Trim: 279mm × 216mm

 Index

DABCO, 49 protection (acetalization), 55 condensation reactions, 213 Danishefsky’s diene, 366 synthesis, 150, 359 (E)-(O)- vs. (Z)-(O)-stereochemistry, Darzens reaction, 134 DIPAMP, 118 204 DBN, 315 DIP-Cl (B-chlorodiisopino- intramolecular alkylation, 194, 199 DBU, 50, 315, 331 campheylborane), 106 kinetic vs. thermodynamic, 188 DCC, 63, 125 1,3-dipolar cycloaddition reactions, 375 enones DDQ, 49 disiamylborane, 126, 162, 165, 296 conjugate reduction, 93, 119, 191 DEAD (diethyl azodicarboxylate), 63, dissolving metal reductions, 119, 191 protection, 58 99 dissonant pattern, 4 synthesis, 213, 249 decalin, 31, 117 1,3-dithianes, 7, 272 transposition, 79 decarboxylation, 177, 183, 306 diynes, 161, 303 enynes, 161 demercuration, 131 DMAP (4-(N,N- enzymatic reductions, 108 deoxygenation, via reduction of dimethylamino)pyridine), epoxidation propargylic carbonate, 307 49 alkenes, 133 thioacetals, 61 DMDO (dimethyldioxirane), 137, 143 allylic alcohols, 144 tosylates, 54, 90 DMPU (N,N’-dimethylpropyleneurea), epoxides tosylhydrazones, 91 185, 232 reactions xanthates, 316 Doebner condensation, 179 acid-catalyzed ring opening, 142 Dess–Martin periodinane (DMP), 74 domino reactions, 18, 179, 181 base-induced elimination, 142 destabilization energies, 25 double asymmetric induction, 100, 148, intramolecular ring-opening, 143 desymmetrization, 108 211 Lewis acid-mediated DHQ, DHQD, 152 rearrangement, 144, 149 DIAB, 254 E1 eliminations, 313 nucleophilic ring-opening, 41, 148 dianions E2 eliminations, 314 with organocopper reagents, 245, carboxylic acid, 140, 186 reactivity and product differentiation 322 β-keto ester, 183 in, 39 synthesis, from propargylic, 347 eclipsed conformation, 21 alkenes, 133, 144 diastereomeric excess (de), 86 ß-effect (carbocation stabilization), halohydrins, 138 diastereotopicity, 100 265 ketones, 138 diazomethane, 63 18 electron rule, 286 Eschenmoser–Claisen rearrangement, DIBAL-H, 91, 96, 143, 319 electronegativity values, 228 341 1,3-dicarbonyl compounds, 175 electrophilic reducing agents, 91 Eschenmoser salt, 213 dichloromethyl methyl ether reaction, ß-elimination reactions, 190, 313 ester enolates, alkylation of, 185 259 elimination reactions esters dicyclohexylborane, 82, 127, 162 alkene synthesis, 313 in alcohol protection, 54 Dieckmann condensation, 180 alkyne synthesis, 343 in carboxyl group protection, 63 Diels, Otto, 365 enamines, 197 pyrolysis of, 316 Diels–Alder reaction, 365 enantiomeric excess (ee), 86 reduction, 86, 91, 96 asymmetric, 373 enantioselective reactions, see synthesis, via intramolecular, 371 asymmetric reactions aldehyde oxidation, 81 Lewis acid–catalyzed, 368 enantiotopicity, 100 allylic alcohol oxidation, 81 regiochemistry, 368 enediyne, 301, 303 carboxylic acid esterification, 63 stereochemistry, 369 enol ethers Claisen rearrangement, 338 digonal, 194 acyl anion equivalent, 11 enamine acylation, 199 dihydroxylation, 150 dihydropyran, 52, 235 enol ether ozonolysis, 124, 157 asymmetric, 152 hydrolysis, 123, 184 enolate acylation, 181, 191 osmium tetroxide, 150 α-metalation, 11, 234 esterification, rate of, 37 Woodward procedure, 152 2-methoxypropene, 53, 55 ethane, 21 diisobutylaluminum hydride, 91, 96, 143, ozonolysis of, 157 ethers, in alcohol protection, 48 319 silyl, 188, 191, 202, 250 Evans aldol reaction, 209 diisopinocampheylborane, 127, 129 synthesis via Birch reduction, diketene, 180, 340 123 Farnesol, 321 1,3-diketones, 183 enol phosphates, 248, 345 Felkin–Anh model, 101 dimethylborolane, 130 enol triflates, 290, 300, 302 Fetizon’s Reagent, 77 dimethyloxosulfonium methylide, 139 enolates, 175 formyl anion equivalents, 7 dimethylsulfonium methylide, 138 alkylation, 185 Franck–Condon effect, 39 dimsyl anion, 138, 325 amide-derived, 186 frustratedLewispair(FLP),119 1,2-diols boron, 207 Fuchs alkynylation, 347 oxidation, 74 C-vs.O-alkylation, 184 functional group interconversion, 15 oxidative cleavage, 158 carboxylic acid–derived, 186 Furakawa reagent, 255 JWST793-bind JWST793-Zweifel February 21, 2017 22:25 Printer Name: Trim: 279mm × 216mm

Index 

Gauche conformation, 22 ß-hydroxy ketones, reduction of, 103 enzymatic, 108 Gilbert reagent, 349 Hhydrozirconation, 294 hydroxyl-directed, 103 Gilman reagents, 242 in presence of aldehydes or esters, Glaser reaction, 303 IBX, 74, 250 95 glycols, formation and cleavage, 157, 359 imine anions, 196 synthesis, via Gold catalysis, 274 indane reduction, 124 acid chlorides, 244 Grignard, Victor, 236 intramolecular reactions alcohol oxidation, 71 Grignard-copper reagents, 242 aldol reaction, 194, 200 alkene cleavage, 155, 124 Grignard reagents, 236 alkylation, 192 alkyne hydration, 165 Grubbs, R., 376 cation-π cyclization, 361 allylic oxidation, 83 Grubbs catalyst, 376 Diels–Alder cycloaddition, 371 carbonylation, 257 diester condensation cyanidation, 258 Hajos–Parrish reaction, 220 acyloin, 181, 355 enol ether hydrolysis, 123 halohydrins, 40, 138 Dieckmann, 180 ß-ketosilane alkene synthesis, 333 halolactonization, 153 epoxide cleavage, 140, 144, 148, 190 kinetic enolate formation, 189 Hammond postulate, 36 free radical cyclizations, 361 kinetic resolution, 150 Hassel, Odd, 21 halonium ion capture, 153 Knoevenagel condensation, 178 Heck, Richard, 288 Heck reaction, 290 Kocienski-modified Julia olefination, Heck reaction, 288 hydroarylation, 274 335 Henry–Nef reaction, 9 metathesis, 375 Krapcho decarboxylation, 177, 183, 306 heterocuprate reagents, 242 Michael addition, 216, 254 Kraus–Pinnick oxidation, 81 HMPA (hexamethylphosphoramide), oxymercuration, 132 K-selectride (potassium tri-sec- 185, 189, 232 Prins reaction, 269, 362 butylborohydride), 90, 97, 191 homochirality, 86 Wittig reaction, 327 homocuprate reagents, 242 iodoform, 252 lactones, from homolytic disconnections, 2 iodolactonization, 153 Baeyer–Villiger oxidation, 135 Horner—Wadsworth–Emmons reaction, iodotrimethylsilane, 48 lactol oxidation, 77 329 Ireland–Claisen rearrangement, 341 Larock annulation, 292 Hoveyda–Grubbs catalyst, 376 isopropylidene acetals, 55 latent polarity, 4 Huang–Minlon reduction, 62 LDA (lithium diisopropylamide), 185, Hudrlik–Peterson diene synthesis, Jacobsen epoxidation, 150 232 271 Jasmone synthesis, 9 lead tetraacetate, 159 Hunsdiecker reaction, 16 Johnson ortho-ester rearrangement, 340 Lemieux–Johnson oxidation, 157 hydantoin, 155 Jones reagent, 72 Lewis acid–catalyzed reactions hydration, of Josiphos, 247 aldol reaction, 211 alkenes, 125 Julia olefination, 334 allylic alcohol epoxidation, 145 alkynes, 11, 165 Kocienski modification of, 335 allylsilane addition, 269 hydrazone anions, 196 hydration, 11, 166 hydrazones, 62, 91, 197, 336 KAPA, 348 MOM ether cleavage, 53 hydrindane, 30 Katsuki, T., 146 Mukaiyama aldol, 202 hydroalumination, 293, 319 ß-keto esters Diels–Alder, 371, 373 hydroamination, 132 alkylation, 182 epoxide rearrangement, 144, 149 hydroboration, of decarboxylation, 183 ligand coordination number, 285 alkenes, 125 preparation Lindlar catalyst, 160, 319 alkynes, 162, 165, 296, 319 of acetoacetic esters, 180 Lipschutz reagents, 242 enynes, 162 by C-acylation, 181 Lithium alkynylides, preparation, 236, hydrogen peroxide, 136, 156, 210 by Claisen condensation, 179 345 hydrogenation by Dieckmann condensation, 180 Lithium aluminum hydride, 86 of alkenes, 115 ketone enolates, 187, 195 Lithium borohydride, 89 of alkynes, 160 ketones Lithium hexamethyldisilazide (LHMDS), asymmetric, 118 deoxygenation, 61 187, 190, 232 directed, 117 deprotonation, 187 Lithium 2,2,6,6-tetramethylpiperidide metal-free, 119 diastereo- and enantiotopicity, 100 (LTMP), 232 hydrogenolysis, of epoxide preparation from, 138 Lithium tri-t-butoxyaluminum hydride, allylic groups, 117 methyl ketone syntheses, 167, 208 87, 94, 97 benzylic groups, 49, 117 protection, 56 Lithium triethoxyaluminum hydride, 88, cyclopropanes, 23 reduction 186 halides, 154 diastereoselective, 97 L-selectride (lithium tri-sec- thioacetals, 61 dissolving metal, 120 butylborohydride), 90, 97 hydrosilylation, 266 enantioselective, 104 Luche reagent, 94 JWST793-bind JWST793-Zweifel February 21, 2017 22:25 Printer Name: Trim: 279mm × 216mm

 Index

macrolactonization, 64 nitriles in palladium-catalyzed cross-coupling magnesium monomethyl malonate, 182 alkylation, 186 reactions, 292, 303 malonic acid esters, 176 intramolecular, 141 preparation, 252 Mander’s reagent, 181 pKa values, 10, 176 reactions, 253 manganese acetate, 79, 83 reduction (DIBAL-H), 92 organozirconium reagents, 294 manganese dioxide, 76, 81 nitroalkanes, 9 ortho ester Claisen rearrangement, 340 Mannich reaction, 213 NMO (N-methylmorpholine-N-oxide), ortho esters, in carboxyl protection, 66 Markovnikov hydration of alkenes, 151 ortho-lithiation, 235 131 norbornane, 32 osmium tetroxide Martin sulfurane, 315 Noyori acetalization, 58 in alkene dihydroxylation, 150 Matteson’s boronic ester homologation, Nozaki–Hiyama reaction, 251 in alkene oxidative cleavage, 157 259 Nozaki–Takai–Hiyama–Kishi coupling, oxaphosphetane, 325 McMurry reaction, 360 252 oxazaborolidines mCPBA (meta-chloroperoxybenzoic nucleophilic reducing agents, 86 in asymmetric Diels–Adler reactions, acid), 133 374 Meerwein–Ponndorf–Verley reduction, OBO ortho ester, 66 in reduction of aldehydes or ketones, 97 Ohira–Bestmann reagent, 349 106 Meinwald rearrangement, 144 Olefin metathesis, 375 oxazolidinones, 209 Meldrum’s acid, 179 open transition state, 202 oxazoline, 65 mercuronium ion, 131 Oppenauer oxidation, 97 oxidation, of mesylates organoalanes, 293, 319 acyloins, 79 based-induced elimination, 313 organoboranes, oxidation of, 129 alcohols, 71 preparation, 314 organoboron reagents, 256 aldehydes, 80 reduction, 54 in asymmetric crotylboration, 261 alkanes, 137 metalation, 231 in cyanidation, 258 alkenes (allylic), 82 of 1-alkynes, 236, 345 in dichloromethyl methyl ether alkynes, 81 allylic or benzylic, 233 reaction, 259 enones, 136 of α-heteroatom substituted alkenes, in Matteson’s boronic ester ketones, 135 234 homologation, 259 organoboranes, 129 p-methoxybenzyl (PMB), 49 in Suzuki reaction, 295 organomercury compounds, 132 methoxymethyl (MOM), 52 organocatalysis, 212, 214, 220, 358, 364, oxidative addition, 287 p-methoxyphenyl (PMP), 47 374 oxone, 74, 81, 137, 158 methyl ketones, preparation of, 167, 208 organocerium reagents, 240 oxymercuration Michael addition, 215 organochromium reagents, 251 of alkenes, 131 disconnections in, 12 in alcohol oxidation, 71 of alkynes, 166 intramolecular, 216 organocopper reagents, 241 ozonolysis, 155 in Robinson annulation, 217 higher-order cyanocuprates stereoelectronic factors in, 39 (Lipshutz), 242 palladium-catalyzed coupling reactions, Michael-type reactions, 178 homocuprates (Gilman), 242 285 MIDA boronate, 296 in ketone preparation, 208, 244 allylic substitution, 304 Mitsunobu reaction, 63, 98, 125, 336 reactions of, 243 Cadiot–Chodkiewicz reaction, 304 MMPP (magnesium organogold chemistry, 274 Castro–Stevens reaction, 302 monoperoxyphthalate), 133 organolithium reagents, 227 conjugated enediyne synthesis, 303

monoisopinocampheylborane (IpcBH2), conjugate addition reactions of, 65, Glaser reaction, 303 130 236 Heck reaction, 288 Mukaiyama reaction, 202 crotyllithium, 233 ß-hydride elimination, 287 MVK (methyl vinyl ketone), 18, 216, organomagnesium reagents, 236 Larock annulation, 292 218 organomercury compounds, 132 Negishi reaction, 292 organopalladium species, 286 oxidative addition, 287 NBS, 155, 320 organosilicon reagents, 264 Sonogashira reaction, 302 NCS, 74 acylsilanes, 272 with sp-carbons, 301 Nef reaction, 9 alkenylsilanes, 266 Stille reaction, 299 Negishi, Ei-ichi, 292 alkynylsilanes, 265 Suzuki reaction, 295 Negishi reaction, 292 allylsilanes, 268 transmetalation, 288 NHC ligand, 286, 295 electronegativity, 264 Trost–Tsuji reaction, 304 NHS, 75 α- and ß-stabilization, 265 Payne rearrangement, 149 Ni-boride, in organotin reagents, in Stille reaction, PCC (pyridinium chlorochromate), 73, hydrogenation, 116 299 80, 129 thioacetal reduction, 61 organotitanium reagents, 239 PDC (pyridinium dichromate), 73, 80 NIS, 250 organozinc reagents pericyclic reactions, 364 JWST793-bind JWST793-Zweifel February 21, 2017 22:25 Printer Name: Trim: 279mm × 216mm

Index 

periodate oxidation, 157, 209, 317 linear vs. convergent synthesis, 17 stereoelectronic effects, 36 peroxy acids, 133, 317 synthetic equivalents, 2 stereogenic carbon, 86 petasis reagent, 240, 326 synthons, 2 stereoisomers, 36, 86 Peterson olefination, 271, 332 Umpolung in, 6 stereoselective reactions, 36, 85 phosphine ligands, 286 Rieke magnesium, 236 stereospecific reactions, 36, 85 phosphonate reagents, 329 Rieke zinc, 161, 303 steric strain, 22 Pinacol coupling, 359 ring-closing olefin metathesis, 15, 375 Stetter reaction, 10, 358 α-pinene, 127 Robinson, Robert, 218 Still–Gennari olefination, 331 pKa values, 176, 231 Robinson annulation, 217 Stille reaction, 299 PLE (porcine liver esterase), 178 Rochelle’s salt, 86 sulfoxides, pyrolysis of, 317 polycyclic ring systems, 30 Rosenmund reduction, 87 sulfur ylides, 138 potassium caroate, 137 Rubottom oxidation, 79 super base, 233 potassium hexamethyldisilazane ruthenium tetroxide, 159 superhydride, 54, 90, 143 (KHMDS), 141, 190, 192, 331 Suzuki, Akira, 295 potassium permanganate, 152 Saegusa–Ito oxidation, 250 Suzuki reaction, 295 PPTS, 52 samarium iodide, 359 Swern oxidation, 73 Prins reaction, 268, 362 Schlenk equilibrium, 237 synthetic equivalents, 2 prochiral centers, 85 Schlosser-modified Wittig olefination, Synthon, 2, 176 propane, 22 327 propargylic alcohols, reduction of, 164 Schlosser’s base, 233 tandem reaction, 18, 200 protective groups, of Schmidt reaction, 132 TBAF, 50 alcohols, 48 Schrock, R., 376 TBHP, 82, 137, 146 carbonyl groups in aldehydes and Schwartz reagent, 294 Tebbe reagent, 240, 326 ketones, 56 secondary orbital overlap, 370 TEMPO, 78 carboxyl groups, 62 selectivity, terminology of, 36, 85 tetrahydropyrans, conformations of, 29 diols, 55 selenium dioxide, 82 tetrahydropyranyl (THP) ethers, 52 NH groups, 45 selenoxides, syn-elimination of, 317 tetramethylammonium triple bonds, 66 Seyferth–Gilbert reagent, 349 triacetoxyborohydride, 104 pyridinium chlorochromate (PCC), 73 Shapiro reaction, 336 TFDO, 137 pyridinium dichromate (PDC), 42, 73 sharpless, K.B., 146 thermodynamic enolate formation, 188 pyrolysis, 316 sharpless asymmetric dihydroxylation, thexylborane, 126, 258 152 thioacetals, reduction of, 61 quinidines, 152 sharpless asymmetric epoxidation, 146 thioester, 208, 210 quinones, 84, 250, 366 resolution of racemic allylic alcohols, TMEDA (tetramethylethylenediamine), 150 230, 232 Ra-Ni (Raney-nickel), 61, 116, 154 Si face, 99 torsional strain, 22 Rawal’s diene, 366 [3,3]-sigmatropic rearrangement, 338 tosyl hydrazone, 62, 91, 336 RCM, 15, 375 silver carbonate, 77 tosylates, preparation of, 314 Re face, 99 silver oxide, 80 TPAP (tetrapropylammonium Red-Al, 88, 149, 165 silyl enol ethers, 60, 188, 191, 202, 250 perruthenate), 75, 99 reduction, of silyl esters, in carboxyl protection, 65 transition states, early vs. late, 36 alkenes, 115 silyl ethers, 50 transmetalation, 288, 300 alkynes, 160 silyl ketene acetal, 212, 214 Trapp mixture, 230 aromatic compounds (dissolving α−silyloxyketones, in aldol reactions, 208 tri-n-butyltin hydride metal), 121 Simmons–Smith cyclopropanation, 255 in halide reduction, 154 carbonyl groups, 85 skew conformation, 21 in thioacetal reduction, 61

chemoselective, 93 SN2-type reactions, 38, 141, 243 in xanthate reduction, 317 enantioselective, 104 sodium amalgam, 216, 334 trichloroacetimidates, 49 cyclic ketones, 97 sodium bis(2-methoxyethoxy)aluminum triflating agents, 53, 290, 300 cyclopropanes, 23 hydride, 88, 149, 165 trifluoroacetic acid (TFA), 47, 291

enones, 93, 95, 116, 119 sodium borohydride, 88, 96, 132 trifluoromethanesulfonimide (Tf2NH), enzymatic, 108 sodium chlorite, 80 374 nitriles, 88, 92 sodium cyanoborohydride, 90, 143 triisopropylsilyl ethers, 51 tosylates, 54, 90 sodium hypochlorite, 78, 138, 150 trimethylsilyl ethers, 50 vinyl esters, 1,2: 92, 1,4: 120 sodium periodate, 159 trimethylsilyl iodide, 48 reductive amination, 91 sodium triacetoxyborohydride, 91 triphenylcarbenium tetrafluoroborate, 79 reductive elimination, 287 solvomercuration–demercuration, 131 trisylhydrazones, 337 Reformatsky reaction, 253 Sonogashira reaction, 302 trityl ethers, 49 retrosynthetic analysis, 1 sparteine, 234, 261 Trost–Tsuji reaction, 304 carbon skeleton construction in, 11 staggered conformation, 21 twistboatconformation,24 JWST793-bind JWST793-Zweifel February 21, 2017 22:25 Printer Name: Trim: 279mm × 216mm

 Index

U values, for substituted cyclohexanes, Wilkinson’s catalyst, 117 xanthates, pyrolysis of, 316 27 Williamson ether synthesis, 48 Umpolung, 6 Wittig,Georg,324 Yamaguchi macrolactonization, Wittig reaction, 324 64 Vilsmeier–Haack formylation, 125 Schlosser modification, 327 ylides vinyl boranes, protonolysis of, 162 ylides phosphonium, 324 vinyl halide synthesis, 288, 320 nonstabilized, 324 sulfonium, 138 vinyl silanes, 266 stabilized, 328 vinyl triflates, 290, 300, 302 Wolff–Kishner reduction, 62 Zimmerman–Traxler transition state

VO(acac)2, 145 Woodward–Hoffmann rules, model, 206, 212 365 zinc borohydride, 89, 91, 95 Wacker oxidation, 167 Woodward procedure for zinc carbenoids, 255 Weinreb amide, 210 syn-dihydroxylation, 152 zirconium reagents, in hydrozirconation, Wieland–Miescher ketone, 59 Wurtz coupling, 229 294