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© Cambridge University Press Cambridge Cambridge University Press 0521770971 - Modern Methods of Organic Synthesis W. Carruthers and Iain Coldham Index More information Index acidity 1 from alkynes 125–32 acyl anion equivalents 56 from diols 123 acyloin reaction 425 from hydrazones 120 Adams’ catalyst 407 reaction of AD-mix ␣ 352 with carbenes 303–9 AD-mix ␤ 352 with dienes in Diels–Alder reaction 162 agelastatin A 376 with radicals 280–98 AIBN 268 reduction of 322, 408–13, 459 alane 437, 444 alkenyllithium species 57, 59 alcohols alkylation 1–19 deoxygenation 270 asymmetric 37 from alkenes 323, 349 with enamines 1, 17 from carbonyl compounds 416, 421, 423, 434–56 with enolates 1–16 oxidation 378–93 with metalloenamines 16 aldehydes alkyl halides alkylation of 17 oxidation to carbonyl compounds 384 as dienophiles in Diels–Alder reaction 169 reductive cleavage to hydrocarbons 269, 406, 442 decarbonylation of 419 alkyllithium species 46 from alcohols 380 alkynes from alkenes 325, 360, 364 conversion to alkenes 125–32, 414 oxidation of 392 deprotonation of 58 reduction of 435, 439, 443 hydrometallation 128 reductive dimerization of 148, 425 preparation of 137 Alder–ene reaction 231 reduction of 125 aldol reaction 27–36 allopumiliotoxin 58 diastereoselective 32 allosamidin disaccharides 272 enantioselective 41 allylic organometallics 71–4 aldosterone 276 allylic oxidation 374 alkenes allylic 1,3-strain 26, 73, 351 allylic oxidation of 374 ␲-allylpalladium complexes 98 conversion to alcohols 323 amabiline 220 conversion to ketones (Wacker reaction) 365 ambruticin S 308 epoxidation of 331–46 amino-hydroxylation 358 hydroboration of 315–30 anionic oxy-Cope rearrangement 241 oxidation to diols 349–57 apovincamine 431 oxidative cleavage of 360 Arbuzov reaction 138 ozonolysis of 360 Arndt–Eistert method 309 preparation of aspidosperma alkaloids 199 by elimination reactions 105, 111 asymmetric reactions by fragmentation reactions 118 aldol reaction 41 by metathesis reactions 151 alkylation of enolates 37 by Wittig and related reactions 132–43 allylation of carbonyl compounds 74 from alkenyl phosphates 433 allylic oxidation 376 487 © Cambridge University Press www.cambridge.org Cambridge University Press 0521770971 - Modern Methods of Organic Synthesis W. Carruthers and Iain Coldham Index More information 488 Index asymmetric reactions (cont.) capnellene 236, 263 cycloaddition reactions 183, 202–11, 218, 226 carbenes 85, 299–311 cyclopropanation 305, 307 carbenoids 299 dihydroxylation 352–5 carboalumination of alkynes 132 ene reactions 233 carbocupration of alkynes 131 epoxidation 337–46 carbolithiation 49 epoxide-opening 109 carbonyl ylides 230 hydroboration 321 Caro’s acid 398 hydrogenation 420 carvone 188 organo-catalytic 45, 397 caryophyllene 212 oxidation of alcohols (kinetic resolution) 389 catecholborane 319 palladium-catalyzed 96, 100 CC-1065 292 radical reactions 281 cedrene 295 reduction of alkenes 420 cerium trichloride 47, 438 reduction of ketones 421, 452 cerulenin 217 with chiral organolithium compounds 50 cervinomycin A 262 with enzymes 355, 371, 401, 454 chelation control 64 avarone 373 cheletropic reaction 272–304 avenaciolide 216 ChiraPHOS 420 aza-Cope rearrangement 242 chloramine-T 347, 358 aziridination 346 m-chloroperoxybenzoic acid see mCPBA azomethine ylides 228 N-chlorosuccinimide 273, 383 chromic acid 370, 371, 378, 392 Baeyer–Villiger reaction 398 chromium trioxide 378 bafilomycin A1 385 Chugaev reaction 113 balanol 297 cis-principle, in Diels–Alder reaction 189 Bamford–Stevens reaction 120, 300 Claisen condensation 11, 30 Barton decarboxylation 271 Claisen rearrangement 244–52 Barton deoxygenation 271 Clemmensen reduction 426 Barton reaction 276 cobalt-mediated cyclization 86 Baylis–Hillman reaction 31 Collins’ reagent 376, 380 9-BBN 317 combretastatin A-1 156 Beckmann rearrangement 277 compactin 178 benzene derivatives complex induced proximity effect 60 Birch reduction of 429 conduramine 173 hydrogenation of 414 conduritol A 200 oxidation of 355, 371 Conia reaction 237 benzocyclobutenes 181, 260 coniceine 152, 285 benzoin condensation 57 conjugate addition 19–27, 40, 66, 76 benzoquinones 164, 181, 191, 208, 373 conessine 275 benzylidene acetal, reductive cleavage 462 Cope elimination 113 benzynes 5, 166 Cope rearrangement 239–43 Bergman cycloaromatization reaction 147 Corey–Fuchs reaction 137 BINAP 96, 420 Corey–Kim oxidation 383 BINOL 74, 208, 233 Corey–Winter reaction 124 biotransformations 355, 371, 401, 454 coriolin 87 Birch reduction 427, 430 Cram’s rule see Felkin–Anh model 9-borabicyclo[3.3.1]nonane see 9-BBN cross-metathesis 154 borane 449 cryptone 321 boron enolates 30, 33, 42, 88, 250 cycloaddition reactions Bouveault–Blanc 425 [2+2] 211 brefeldin 60, 253 [2+2+2] 89 brevetoxin B 136 [4+2] see Sections 3.1, 3.3, 3.4 brevicomin 120, 281, 314 Diels–Alder 159–211 BRL-55834 343 dipolar 222–31 B¨urgi–Dunitz angle 36 with allyl anions and cations 219–21 cyclocitral 256 calicheamicins 94, 224, 251 cycloeudesmol 308 calyculin A 320 cyclopropanes camptothecin 291 from carbenes 304 CAN 373 from sulfoxonium ylides 54 © Cambridge University Press www.cambridge.org Cambridge University Press 0521770971 - Modern Methods of Organic Synthesis W. Carruthers and Iain Coldham Index More information Index 489 cyclotrimerization 89 elimination reactions cytovaricin 102 ␤-eliminations 105–10 pyrolytic syn eliminations 111 dactylol 153 enamines 17, 22 Dakin reaction 401 ene reaction 231–8 Danishefsky’s diene 170, 176 enediynes 94, 147 daphniphyllum alkaloids 197 enolates daunoomycinone 182 aldol reaction with 28–36 DBU 109 alkylation with 2–11 DDQ 373 conjugate addition with 19–27 decarbonylation 419 regioselective formation of 7, 12, 14, 16 decarboxylation 6 stereoselective formation of 14, 33, decarestrictine L 257 248 Dess–Martin reagent 389 enol ethers, ␣-lithiation 57 DHQ and DHQD 352 enols 2 dianions 10 enol silanes see silyl enol ether diazocarbonyl compounds 53, 230, 257, 299, 300, enol triflates 80, 90, 91, 93, 97 303, 306–11 enone formation 394 DIBAL-H 437, 445 enzymes see biotransformations dichloromethyllithium 328 EO9 373 Diels–Alder reaction 159–211 epibatidine 270, 388, 439 asymmetric 202 epothilones 153 intramolecular 193 epoxidation 331–46 regioselectivity 185 epoxides retro-Diels–Alder 199 from alkenes 331–46 stereoselectivity 188 from sulfur ylides 53, 310 dienes 174–85 ring-opening 67, 81, 109, 442 dienophiles 162–74 ergosterol 173 diethylzinc 70 Eschenmoser fragmentation 120 dihydroquinidine see DHQD Eschenmoser’s salt 110 dihydroquinine see DHQ Eschweiler–Clark reaction 447 dihydrosterculic acid 305 estradiol 198 dihydroxylation of alkenes 349–57 estrone 260 di-imide 459 Etard´ reaction 372 di-isopinocampheylallyl borane 74 Evans aldol reaction 42 di-isopinocampheylborane 321 di-isopinocampheylboron triflate 43 Felkin–Anh model 36, 47, 69, 440 di-isopinocampheylchloroborane 453 Fetizon’s reagent 386 dimethylsulfonium methylide 53 Fischer carbenes 85 dimethylsulfoxonium methylide 53 Fischer indole synthesis 251 diolmycin 341 FK-506 55, 271 1,2-diols, preparation from alkenes formamidines 49 349–57 FR-900848 305 DIOP 420 FR-901464 128, 211 dioxiranes 336, 344 fragmentation reactions 118–20 DIPAMP 420 fredericamycin A 464 dipolar cycloaddition reactions free radical reactions 268–98 222–31 Fremy’s salt 373 diplodialide A 11 frondosin B 264 dipolarophiles 222 disiamylborane 316 galanthamine 385 disodium prephenate 176 gephyrotoxin 172 dithianes 56 germacrane sesquiterpenes 242 DMDO 336 Gilman reagents 75 D¨otz reaction 85 Glaser reaction 94 DuPHOS 420 glutathione 433 dynemicin A 94 grandisol 369 grayanotoxin 293 ecdysone 99 Grignard reagents 67 echinocandin D 326 Grobfragmentation 118 electrocyclic reactions 259 Grubbs catalyst 151 © Cambridge University Press www.cambridge.org Cambridge University Press 0521770971 - Modern Methods of Organic Synthesis W. Carruthers and Iain Coldham Index More information 490 Index halichlorine 329 from alkynes 323 halogen–lithium exchange 46, 49, 59, 62 oxidation of 394–401 halogen–magnesium exchange 63 reduction of Heck reaction 94 to alcohols 416, 421, 423, 434–56 hemibrevetoxin B 110 to methylene compounds 426, 448, 457, 458, hennoxazole A 146 462 heterodienes in Diels–Alder reaction 183 reductive dimerization of see pinacol reaction hetereodienophiles in Diels–Alder reaction 169 Kharasch–Sosnovsky reaction 376 hirsutene 290 khusimone 236 histrionicotoxin 390 kinetic enolate formation 8, 12, 29, 33 Hofmann–L¨offler–Freytag reaction 273 kinetic resolution Hofmann reaction 107 of allylic alcohols 340 Hofmann rule in eliminations 106 of benzylic alcohols 389 Horner–Wadsworth–Emmons reaction 138 of epoxides 343 Horner–Wittig reaction 140 Knoevenagel condensation 30 hybocarpone 264 Kuhn–Roth estimation 370 hydrazones 19 Kulinkovich reaction 65 hydroalumination 129 hydroboration lactones of alkenes 316–30 from ketones by Baeyer–Villiger reaction 398 of alkynes 127 reduction of, to lactols 445 hydrogenation 405–22 laulimalide 341 hydrogenolysis 406 lavendamycin 201 hydrosilylation 131 lennoxamine 297 hydrostannylation 131 Lewis acids ␣-hydroxy-ketones 396 in addition to aldehydes 68, 70, 73 hydrozirconation 128 in aldol reaction 29 hyellazole 262 in alkylation 13 hypervalent iodine reagents 374, 389, 395, 397 in conjugate addition 23, 76 in Diels–Alder reaction 169, 187 ibogamine 208 in ene reaction 231 IBX 372, 389, 396 in epoxide opening 442 indanomycin 194 in reductions 438, 462 indinavir 368 linalool 259 indolizidines 227 Lindlar’s catalyst 125, 414 iodic acid 396 lipstatin 218 N-iodosuccinimide 278 lithium
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