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