acidity 1
acyl anion equivalents 56
acyloin reaction 425
Adams’ catalyst 407
AD-mix α 352
AD-mix β 352
agelastatin A 376
AIBN 268
alane 437, 444
alcohols
deoxygenation 270
from alkenes 323, 349
from carbonyl compounds 416, 421, 423, 434–56
oxidation 378–93
aldehydes
alkylation of 17
as dienophiles in Diels–Alder reaction 169
decarbonylation of 419
from alcohols 380
from alkenes 325, 360, 364
oxidation of 392
reduction of 435, 439, 443
reductive dimerization of 148, 425
Alder–ene reaction 231
aldol reaction 27–36
diastereoselective 32
enantioselective 41
aldosterone 276
alkenes
allylic oxidation of 374
conversion to alcohols 323
conversion to ketones (Wacker reaction) 365
epoxidation of 331–46
hydroboration of 315–30
oxidation to diols 349–57
oxidative cleavage of 360
ozonolysis of 360
preparation of
by elimination reactions 105, 111
by fragmentation reactions 118
by metathesis reactions 151
by Wittig and related reactions 132–43
from alkenyl phosphates 433
from alkynes 125–32
from diols 123
from hydrazones 120
reaction of
with carbenes 303–9
with dienes in Diels–Alder reaction 162
with radicals 280–98
reduction of 322, 408–13, 459
alkenyllithium species 57, 59
alkylation 1–19
asymmetric 37
with enamines 1, 17
with enolates 1–16
with metalloenamines 16
alkyl halides
oxidation to carbonyl compounds 384
reductive cleavage to hydrocarbons 269, 406, 442
alkyllithium species 46
alkynes
conversion to alkenes 125–32, 414
deprotonation of 58
hydrometallation 128
preparation of 137
reduction of 125
allopumiliotoxin 58
allosamidin disaccharides 272
allylic organometallics 71–4
allylic oxidation 374
allylic 1,3-strain 26, 73, 351
π-allylpalladium complexes 98
amabiline 220
ambruticin S 308
amino-hydroxylation 358
anionic oxy-Cope rearrangement 241
apovincamine 431
Arbuzov reaction 138
Arndt–Eistert method 309
aspidosperma alkaloids 199
asymmetric reactions
aldol reaction 41
alkylation of enolates 37
allylation of carbonyl compounds 74
allylic oxidation 376
asymmetric reactions (cont.)
cycloaddition reactions 183, 202–11, 218, 226
cyclopropanation 305, 307
dihydroxylation 352–5
ene reactions 233
epoxidation 337–46
epoxide-opening 109
hydroboration 321
hydrogenation 420
organo-catalytic 45, 397
oxidation of alcohols (kinetic resolution) 389
palladium-catalyzed 96, 100
radical reactions 281
reduction of alkenes 420
reduction of ketones 421, 452
with chiral organolithium compounds 50
with enzymes 355, 371, 401, 454
avarone 373
avenaciolide 216
aza-Cope rearrangement 242
aziridination 346
azomethine ylides 228
Baeyer–Villiger reaction 398
bafilomycin A1 385
balanol 297
Bamford–Stevens reaction 120, 300
Barton decarboxylation 271
Barton deoxygenation 271
Barton reaction 276
Baylis–Hillman reaction 31
9-BBN 317
Beckmann rearrangement 277
benzene derivatives
Birch reduction of 429
hydrogenation of 414
oxidation of 355, 371
benzocyclobutenes 181, 260
benzoin condensation 57
benzoquinones 164, 181, 191, 208, 373
benzylidene acetal, reductive cleavage 462
benzynes 5, 166
Bergman cycloaromatization reaction 147
BINAP 96, 420
BINOL 74, 208, 233
biotransformations 355, 371, 401, 454
Birch reduction 427, 430
9-borabicyclo[3.3.1]nonane see 9-BBN
borane 449
boron enolates 30, 33, 42, 88, 250
Bouveault–Blanc 425
brefeldin 60, 253
brevetoxin B 136
brevicomin 120, 281, 314
BRL-55834 343
Bürgi–Dunitz angle 36
calicheamicins 94, 224, 251
calyculin A 320
camptothecin 291
CAN 373
capnellene 236, 263
carbenes 85, 299–311
carbenoids 299
carboalumination of alkynes 132
carbocupration of alkynes 131
carbolithiation 49
carbonyl ylides 230
Caro’s acid 398
carvone 188
caryophyllene 212
catecholborane 319
CC-1065 292
cedrene 295
cerium trichloride 47, 438
cerulenin 217
cervinomycin A 262
chelation control 64
cheletropic reaction 272–304
ChiraPHOS 420
chloramine-T 347, 358
m-chloroperoxybenzoic acid see mCPBA
N-chlorosuccinimide 273, 383
chromic acid 370, 371, 378, 392
chromium trioxide 378
Chugaev reaction 113
cis-principle, in Diels–Alder reaction 189
Claisen condensation 11, 30
Claisen rearrangement 244–52
Clemmensen reduction 426
cobalt-mediated cyclization 86
Collins’ reagent 376, 380
combretastatin A-1 156
compactin 178
complex induced proximity effect 60
conduramine 173
conduritol A 200
Conia reaction 237
coniceine 152, 285
conjugate addition 19–27, 40, 66, 76
conessine 275
Cope elimination 113
Cope rearrangement 239–43
Corey–Fuchs reaction 137
Corey–Kim oxidation 383
Corey–Winter reaction 124
coriolin 87
Cram’s rule see Felkin–Anh model
cross-metathesis 154
cryptone 321
cycloaddition reactions
[2+2] 211
[2+2+2] 89
[4+2] see Sections 3.1, 3.3, 3.4
Diels–Alder 159–211
dipolar 222–31
with allyl anions and cations 219–21
cyclocitral 256
cycloeudesmol 308
cyclopropanes
from carbenes 304
from sulfoxonium ylides 54
cyclotrimerization 89
cytovaricin 102
dactylol 153
Dakin reaction 401
Danishefsky’s diene 170, 176
daphniphyllum alkaloids 197
daunoomycinone 182
DBU 109
DDQ 373
decarbonylation 419
decarboxylation 6
decarestrictine L 257
Dess–Martin reagent 389
DHQ and DHQD 352
dianions 10
diazocarbonyl compounds 53, 230, 257, 299, 300, 303, 306–11
DIBAL-H 437, 445
dichloromethyllithium 328
Diels–Alder reaction 159–211
asymmetric 202
intramolecular 193
regioselectivity 185
retro-Diels–Alder 199
stereoselectivity 188
dienes 174–85
dienophiles 162–74
diethylzinc 70
dihydroquinidine see DHQD
dihydroquinine see DHQ
dihydrosterculic acid 305
dihydroxylation of alkenes 349–57
di-imide 459
di-isopinocampheylallyl borane 74
di-isopinocampheylborane 321
di-isopinocampheylboron triflate 43
di-isopinocampheylchloroborane 453
dimethylsulfonium methylide 53
dimethylsulfoxonium methylide 53
diolmycin 341
1,2-diols, preparation from alkenes 349–57
DIOP 420
dioxiranes 336, 344
DIPAMP 420
dipolar cycloaddition reactions 222–31
diplodialide A 11
dipolarophiles 222
disiamylborane 316
disodium prephenate 176
dithianes 56
DMDO 336
Dötz reaction 85
DuPHOS 420
dynemicin A 94
ecdysone 99
echinocandin D 326
electrocyclic reactions 259
elimination reactions
β-eliminations 105–10
pyrolytic syn eliminations 111
enamines 17, 22
ene reaction 231–8
enediynes 94, 147
enolates
aldol reaction with 28–36
alkylation with 2–11
conjugate addition with 19–27
regioselective formation of 7, 12, 14, 16
stereoselective formation of 14, 33, 248
enol ethers, α-lithiation 57
enols 2
enol silanes see silyl enol ether
enol triflates 80, 90, 91, 93, 97
enone formation 394
enzymes see biotransformations
EO9 373
epibatidine 270, 388, 439
epothilones 153
epoxidation 331–46
epoxides
from alkenes 331–46
from sulfur ylides 53, 310
ring-opening 67, 81, 109, 442
ergosterol 173
Eschenmoser fragmentation 120
Eschenmoser’s salt 110
Eschweiler–Clark reaction 447
estradiol 198
estrone 260
Étard reaction 372
Evans aldol reaction 42
Felkin–Anh model 36, 47, 69, 440
Fetizon’s reagent 386
Fischer carbenes 85
Fischer indole synthesis 251
FK-506 55, 271
formamidines 49
FR-900848 305
FR-901464 128, 211
fragmentation reactions 118–20
fredericamycin A 464
free radical reactions 268–98
Fremy’s salt 373
frondosin B 264
galanthamine 385
gephyrotoxin 172
germacrane sesquiterpenes 242
Gilman reagents 75
Glaser reaction 94
glutathione 433
grandisol 369
grayanotoxin 293
Grignard reagents 67
Grob fragmentation 118
Grubbs catalyst 151
halichlorine 329
halogen–lithium exchange 46, 49, 59, 62
halogen–magnesium exchange 63
Heck reaction 94
hemibrevetoxin B 110
hennoxazole A 146
heterodienes in Diels–Alder reaction 183
hetereodienophiles in Diels–Alder reaction 169
hirsutene 290
histrionicotoxin 390
Hofmann–Löffler–Freytag reaction 273
Hofmann reaction 107
Hofmann rule in eliminations 106
Horner–Wadsworth–Emmons reaction 138
Horner–Wittig reaction 140
hybocarpone 264
hydrazones 19
hydroalumination 129
hydroboration
of alkenes 316–30
of alkynes 127
hydrogenation 405–22
hydrogenolysis 406
hydrosilylation 131
hydrostannylation 131
α-hydroxy-ketones 396
hydrozirconation 128
hyellazole 262
hypervalent iodine reagents 374, 389, 395, 397
ibogamine 208
IBX 372, 389, 396
indanomycin 194
indinavir 368
indolizidines 227
iodic acid 396
N-iodosuccinimide 278
ipsdienol 234
Ireland–Claisen rearrangement 248
iridomyrmecin 25
isocaryophyllene 149
isocomene 213, 308
Jacobsen–Katsuki epoxidation 342
jasmone 58, 103
Johnson–Claisen rearrangement 245
Jones’ reagent 378
juglone 373
Julia olefination 144
juvabione 242
juvenile hormone 118, 130
kainic acid 235, 292
kallolide B 253
kamausallene 293
kempene-2 148
ketenes 216
ketones
alkylation of 7
from alcohols 378–92
from alkenes 325, 327, 360, 365
from alkynes 323
oxidation of 394–401
reduction of
to alcohols 416, 421, 423, 434–56
to methylene compounds 426, 448, 457, 458, 462
reductive dimerization of see pinacol reaction
Kharasch–Sosnovsky reaction 376
khusimone 236
kinetic enolate formation 8, 12, 29, 33
kinetic resolution
of allylic alcohols 340
of benzylic alcohols 389
of epoxides 343
Knoevenagel condensation 30
Kuhn–Roth estimation 370
Kulinkovich reaction 65
lactones
from ketones by Baeyer–Villiger reaction 398
reduction of, to lactols 445
laulimalide 341
lavendamycin 201
lennoxamine 297
Lewis acids
in addition to aldehydes 68, 70, 73
in aldol reaction 29
in alkylation 13
in conjugate addition 23, 76
in Diels–Alder reaction 169, 187
in ene reaction 231
in epoxide opening 442
in reductions 438, 462
linalool 259
Lindlar’s catalyst 125, 414
lipstatin 218
lithium aluminium hydride 435
modification of reducing properties by
alcohols 443
aluminium chloride 444
lithium diisopropylamide (LDA) 6
lithium hexamethyldisilazide (LHMDS) 6
lividosamine 223
Lombardo reagent 150
L-selectride 441
Luche reduction 438
luciduline 227
lupinine 197
lycoricidine 172
malyngolide 302
manganese dioxide 384
Mannich reaction 110, 242
manzamine A 196, 214
McMurry reaction 123, 148, 425
mCPBA 331, 398
Meerwein–Pondorff–Verley reduction 434
Meisenheimer rearrangement 259
mesembrine 22, 303
metallocarbenes 299
metalloenamines 19
metallo-ene reaction 235
metathesis of alkenes 151–4
methyl chrysanthemate 155
methyltrioxorhenium 335
Michael reaction 20
minovine 165
Mitsunobu reaction 4
molecular orbital theory
in Diels–Alder reaction 160
mono-isopinocampheylborane 321
MonoPhos 421
MoOPH 396
morphine 292
Mukaiyama aldol reaction 29, 44
muscarine 301
myrtanol 324
naproxen 98, 421
Nazarov cyclization 263
Nef reaction 58
Negishi reaction 69
nemorensic acid 431
Newman projection 36, 47, 64
Nicholas reaction 88
nicotine 367
nitrenes 347
nitrile oxides 223
nitrones 225
nitrosobenzene 397
NMO 350, 387
nonactic acid 221
Nozaki–Hiyama–Kishi reaction 84
oestrone 425
Oppenauer oxidation 392
organoborane compounds 315
organo-catalysis 26, 45, 397
organochromium reagents 81–5, 150, 217, 306
organocobalt reagents 85–9
organocopper reagents 75–81, 131
organolithium species 45–63
organomagnesium reagents 63–7
organomercury compounds 272, 285, 295
organopalladium species 89–101
organozinc reagents 67–71
ortho-lithiation 60
ortho-quinodimethanes 181, 198, 260
Oshima–Lombardo reagent 150
osmium tetroxide 349
Overman rearrangement 252
oxaphosphetane 133
oxazaborolidine 453
oxaziridines 337, 396
oxaziridinium salts 337
oxidation
of aldehydes 392
of alkanes 370
of alkenes 374
of benzenes 371
of alcohols 378–93
of ethers 393
of ketones 394
oxidative cleavage of alkenes 360–4
Oxone® 324, 364
oxy-Cope rearrangement 240
ozonolysis 222, 360
paeonilactone A 80
palladium complexes
π-allyl 98
in coupling reactions 89–101
in metallo-ene reaction 101, 238
in oxidation of alkenes 365
in [3,3]-sigmatropic rearrangements 239, 252
palladium-ene reaction 101, 238
pancracine 243
pancratistatin 252, 355
parviflorin 353
Paternò–Büchi reaction 215
Pauson–Khand reaction 86
PCC 376, 380
PDC 380, 393
penicillins 256
pentalenene 366
perhydrohistrionicotoxin 277
pericyclic reactions 159
periodic acid 393
periplanone-B 142
peroxy acids 331, 398
Petasis reagent 149
Peterson reaction 141
phorboxazole B 462
phosphonium ylides 133
photocycloadditions 211
photolysis 268, 271, 276, 300, 310
phyllodulcin 63
physostigmine 96
phytuberin 363
pinacol reaction 148, 425
pinnaic acid 156
pKa values 1
plicamine 374
podocarpic acid 294
polymer-supported catalysts and reagents 355, 374, 386, 388, 439
polymethylhydrosiloxane (PMHS) 461
potassium permanganate 349, 356, 371, 385
precapnelladiene 214
preussin 215
Prévost reaction 357
prostaglandins 48, 92, 246, 290, 400
pumiliotoxin C 177, 463
pyridinium chlorochromate see PCC
pyridinium dichromate see PDC
pyrolytic eliminations 111
quinidine 31, 218, 250
quinuclidine 31
quinones 164, 373
radicals 268–98
Ramberg–Bäcklund reaction 146
Raney nickel 52, 407, 415, 458
rearrangements
of carbocations 107
of sulfoxides 258
see also sigmatropic rearrangements
reduction
asymmetric 420, 452, 455
dissolving metal 422
of acetals 462
of acid chlorides 443, 460
of aldehydes and ketones 416, 423, 434, 437, 448, 451, 461
of alkenes 408, 459
of alkyl halides 270, 406, 442
of alkynes 125, 414, 432
of aromatics 414, 429
of carboxylic acids 435, 450
of carboxylic amides 435, 444, 445, 451
of enones 427, 438, 461
of epoxides 442, 452
of esters 425, 435, 439, 444, 445, 460
of imines 446
of nitriles, oximes and nitro compounds 416, 444, 445
of sulfonates 442
reductive amination 446
reductive cleavage reactions 432
Reformatsky reaction 68
reserpine 191
reticuline 50
retro Diels–Alder reaction 199
rhodium catalysts 14, 230, 301, 306, 310, 319, 321, 410, 415, 417, 420, 447
rifamycin 324
ring-closing metathesis 152
rishirilide B 182
Robinson annulation 26
Rosenmund reduction 460
ruthenium tetroxide 364, 394
SAE reaction see Sharpless asymmetric epoxidation
samarium diiodide 285, 293
sanglifehrin 37
santalene 168
sarcomycin 199, 224
sarcophytol 425
sarain A 228
Saytzeff elimination 106
Schlenk equilibrium 63
Schlosser’s base 46
Schrock catalyst 151
Schwartz reagent 128
scopadulcic acid A 240
secologanin 164
secondary orbital overlap 192
sedridine 225
selenium dioxide 374
selenoxides 116
self-regeneration of chirality
septorin 103
sesquicarene 308
Shapiro reaction 121
Sharpless asymmetric dihydroxylation 352
Sharpless asymmetric epoxidation 338
shikimic acid 178, 207
sigmatropic rearrangements
[2,3] 253–9
[3,3] 238–52
silver carbonate oxidation of alcohols 386
silyl enol ethers 11–14, 23, 29, 248, 460
Simmons–Smith cyclopropanation 272–304
slaframine 171
SN2 4, 79
sodium borohydride 435
sodium chlorite 393
sodium cyanoborohydride 446
sodium triacetoxyborohydride 447
solenopsin 225
Sommelet–Hauser rearrangement 257
Sonogashira reaction 93
sparteine 50, 389
squalene 52
Staudinger reaction 218
Stevens rearrangement 256
Still–Wittig reaction 140
Stille reaction 90
strychnine 41, 96, 243, 251
Stryker’s reagent 461
sulfones 55, 144, 166, 198, 284, 433
sulfoxides 115, 167, 177, 258
sulfur ylides 53, 310
Suzuki reaction 92, 329
Swern oxidation 382
TADDOL 208
Takai olefination 150
taxanes 194, 359, 387
tazettine 96
Tebbe reagent 149
tedanolide 394
TEMPO 391, 393
terpineol 204
tetra-n-propylammonium perruthenate see TPAP
thermodynamic enolate formation 8, 16, 21, 29
thexylborane 317
thienamycin 303
Thorpe–Ingold effect 288
tin–lithium exchange 51, 59
titanium reagents 29, 31, 34, 41, 44, 52, 58, 74, 123, 148, 208, 233, 338, 425
toxol 410
TPAP 387
transfer hydrogenation 406
trialkylsilanes as reducing agents 460
tributyltin hydride 188, 269, 270, 281, 288, 295
tris(trimethylsilyl)silane 284
tumerone 13
tylonolide 270
umpolung 56
unactivated C–H bonds, functionalization of 272–278
α,β-unsaturated carbonyl compounds
alkylation of 15, 16
as dienes in Diels–Alder reactions 164, 183
as dienophiles in Diels–Alder reactions 162
as dipolarophiles 226
deconjugative alkylation of 14, 77
in conjugate addition reactions 19–27, 40, 75
in photocycloaddition with alkenes 211
preparation by allylic oxidation 374, 376
reduction to alkenes 433, 437, 438, 445, 446, 448, 458
reduction to the saturated carbonyl compound 409, 410, 418, 420, 427, 461
Upjohn dihydroxylation 350
valerane 77
vanadium acetylacetonate 334
vancomycin 369
vernolepin 279
vitamin D 173, 179
Wacker oxidation reaction 365
Wadsworth–Emmons reaction 138
Weinreb amide 65
widdrol 249
Wilkinson’s catalyst 319, 417, 460
Wittig reaction 132–41
Wittig rearrangement 253
Wolff–Kishner reduction 457
Wolff rearrangement 309
Woodward–Hoffmann rules 160, 192, 219, 259
Woodward–Prévost reaction 357
xanthates, in pyrolysis to give alkenes 111, 113
ylides
phosphonium 133
sulfonium 53, 310
Zaitsev elimination 106
zampanolide 157
zearalenone 90
Zimmerman–Traxler model 32, 41
zinc, as reducing agent 423, 426