Electrophilic cyclization (cont.)
integramycin model, 228, 229
Endocyclic enol ether
acid-catalyzed cyclizations
attenol A and didemnaketal B,
209, 210
Suzuki–Miyaura coupling approach,
210
chiral acid-catalyzed spirocyclizations
(S)-and(R)-TRIP for spirocyclization,
212
chiral phosphoric acids, 212
C ˇ oric ´ and List approach, 212
imidophosphate dime, 212, 213
intramolecular oxymercuration, 214
ent-Amphidinolide V, 377, 378
Enterobactin, 406–407
Epilachnene, 377–378, 384
Epothilones, 378–380, 384–385
Epoxides
formation
opening with carbon nucleophiles,
361–362
opening with oxygen nucleophiles,
360–361
rearrangement, 360–363
opening
bryostatins, 61
phorboxazole A, 60
stereochemical consequences, 59–60
ring opening, 237, 284–288
aryl substitution effect, 235, 237
carbohydrate-derived epoxides, 234
epoxidation–spirocyclization method,
236
intramolecular epoxide ring-opening
reaction, 238
mono(benzannulated) spiroacetals, 239
sawaranospirolides, 236, 237
3’6’-Epoxyauraptene, 146, 147
Etherification, 169
Ethers
cleavage, 146
eight-to ten-membered ring
carbon–carbon double bond, metathesis,
323–344
carbon–carbon single bond formation,
344–351
carbon–oxygen single bond formation,
351–355
epoxides formation, 360–363
ring expansion and rearrangement,
355–359
medium-sized ethers, 322
seven-membered ring ethers (see
Seven-membered ring ethers)
vetiver oil, 149
Ethisolide, 178–180
Evans aldolization, 106–107
Exocyclic enol ether, 214–215
Goekjian approach, 214, 215,
iodoetherification/Ag-catalyzed
cyclization, 215
sulfone lithiation approach, 216
F
FR-901, 422–423
Friedel–Crafts reaction, 295–298
Frontier molecular orbital (FMO) theory, 46
Furan
description, 162–165
oxidation
crassalactone D and pyrenolide D,
246, 247
sawaranospirolides, 247
5,5-spirolactones, 246, 248
reductions, 26–27
Fuwa and Sasaki’s synthesis, 209
G
Gauche effect, 325, 326
Giese and Gerth synthesis, δ-lactones, 101, 102
(–)-Gloeosporone, 410–411
Glycinoeclepin, 153–158
(–)-Grahamimycin A1, 408, 409
H
(+)-Halichlorine, 418, 419
Halolactonization, 124–125, 313
2-Halomethyl cyclic ethers, 289
Heathcock and Chavdarian synthesis,
δ-lactones, 100, 101
Hemiacetal reductions, 2
Hemiacetal spirocyclization, 205, 206
auripyrones A and B, 206, 207
berkelic acid, 206, 208
Henryon and Fe ´re ´zou’s approach,
205, 206
pteridic acid A, 206, 207
Heterocyclization, metal-mediated, 353–354
Hetero-Diels–Alder (HDA) reactions, 122
Chiral acetonide dienophiles, 82, 83
Cr(III)-catalyzed, 83, 84
432
Index
integramycin model, 228, 229
Endocyclic enol ether
acid-catalyzed cyclizations
attenol A and didemnaketal B,
209, 210
Suzuki–Miyaura coupling approach,
210
chiral acid-catalyzed spirocyclizations
(S)-and(R)-TRIP for spirocyclization,
212
chiral phosphoric acids, 212
C ˇ oric ´ and List approach, 212
imidophosphate dime, 212, 213
intramolecular oxymercuration, 214
ent-Amphidinolide V, 377, 378
Enterobactin, 406–407
Epilachnene, 377–378, 384
Epothilones, 378–380, 384–385
Epoxides
formation
opening with carbon nucleophiles,
361–362
opening with oxygen nucleophiles,
360–361
rearrangement, 360–363
opening
bryostatins, 61
phorboxazole A, 60
stereochemical consequences, 59–60
ring opening, 237, 284–288
aryl substitution effect, 235, 237
carbohydrate-derived epoxides, 234
epoxidation–spirocyclization method,
236
intramolecular epoxide ring-opening
reaction, 238
mono(benzannulated) spiroacetals, 239
sawaranospirolides, 236, 237
3’6’-Epoxyauraptene, 146, 147
Etherification, 169
Ethers
cleavage, 146
eight-to ten-membered ring
carbon–carbon double bond, metathesis,
323–344
carbon–carbon single bond formation,
344–351
carbon–oxygen single bond formation,
351–355
epoxides formation, 360–363
ring expansion and rearrangement,
355–359
medium-sized ethers, 322
seven-membered ring ethers (see
Seven-membered ring ethers)
vetiver oil, 149
Ethisolide, 178–180
Evans aldolization, 106–107
Exocyclic enol ether, 214–215
Goekjian approach, 214, 215,
iodoetherification/Ag-catalyzed
cyclization, 215
sulfone lithiation approach, 216
F
FR-901, 422–423
Friedel–Crafts reaction, 295–298
Frontier molecular orbital (FMO) theory, 46
Furan
description, 162–165
oxidation
crassalactone D and pyrenolide D,
246, 247
sawaranospirolides, 247
5,5-spirolactones, 246, 248
reductions, 26–27
Fuwa and Sasaki’s synthesis, 209
G
Gauche effect, 325, 326
Giese and Gerth synthesis, δ-lactones, 101, 102
(–)-Gloeosporone, 410–411
Glycinoeclepin, 153–158
(–)-Grahamimycin A1, 408, 409
H
(+)-Halichlorine, 418, 419
Halolactonization, 124–125, 313
2-Halomethyl cyclic ethers, 289
Heathcock and Chavdarian synthesis,
δ-lactones, 100, 101
Hemiacetal reductions, 2
Hemiacetal spirocyclization, 205, 206
auripyrones A and B, 206, 207
berkelic acid, 206, 208
Henryon and Fe ´re ´zou’s approach,
205, 206
pteridic acid A, 206, 207
Heterocyclization, metal-mediated, 353–354
Hetero-Diels–Alder (HDA) reactions, 122
Chiral acetonide dienophiles, 82, 83
Cr(III)-catalyzed, 83, 84
432
Index