Carba-pyranose, 167
Carbon–carbon bonds cleavage, 177–182
Carbon–carbon double bond, metathesis
applications, 323–344
discovery and development, 323
eight-membered oxacycles synthesis
benzooxocin ring system, 331
Brevetoxin A, 334
Claisen–Ireland rearrangement, 330
conformational reorganization, 328
CTX3C synthesis, 334
enantioselective total synthesis,
331, 332
gauche effect, 326
heliannuols, benzooxocin core,
331, 332
Laurencia oxacycles, 325
(+)-laurencin, 325
octalactins, 332, 333
(+)-prelaureatin, 327, 328
RCM, protecting groups, 327, 328
relative stereochemistry, 329, 330
solandelactones, cyclopropyl lactone,
333, 334
tributylstannyl group, 329, 330
Grubbs catalyst, 325
metathesis catalysts examples, 323, 324
nine-membered oxacycles synthesis
eleutherobin, B-ring, 336, 337
formation, 335, 336
gambieric acids, 340
(–)-halicholacton, 338
halicholactone, 337
isolaurallene synthesis, 335, 336
(+)-obtusenyne synthesis, 336, 337
oxoninoquinolones, 336, 338
polycyclic ether skeletons, 340, 341
relative stereochemistry effect,
339, 340
topsentolide B 3 , stereoselective
synthesis, 338, 339
olefin metathesis, 323
ten-membered oxacycles synthesis
C1–C7 fragment synthesis, 341, 342
description, 341
microcarpalide synthesis, 342
olefin geometry, catalyst effect,
343–344
Carbon–carbon single bond formation
anion alkylation, 347–349
anionic cyclization, 298–300
cycloaddition and pericyclic reaction,
349–350
electrophilic cyclization, 295–298
free radical cyclization, 344–346
metal-induced cyclization, 300–306
metal-mediated cyclization, 346–347
photochemical processes, 310–311
Prins-type reaction cyclization, 350–351
radical reactions, 307–310
thermal cycloadditions and rearrangements,
306–307
Carbon–oxygen single bond formation
enamide halo-etherification, 352
epoxides ring opening, 291–292
hydroxy ketones and thioketals, 351–352
hydroxyl allene, intramolecular
cyclization, 353
hydroxyl ketones, reductive cyclization,
292–293
metal-mediated heterocyclization, 353–354
oxa-Michael reactions, 294–295
oxygenated nucleophiles, 288–291
pericyclic reaction, 355
polyenes oxidation, 291–292
Ullmann coupling, 293, 294
Carbonylation, lactones, 129–130
Carboxylation, lactones, 130–131
Carotenoid pigment, 158–159
C2–C3 THP-forming processes
Panek [4+2]-annulation strategies
2,6-cis DHP, 74
leucascandrolide A, 74, 75
(+)-SCH 351448, 75
stereoselective annulation method,
73, 74
Petasis–Ferrier union/rearrangement
mechanism of, 71
phorboxazole A, 72
spongistatin 1, 73
trisubstituted alkenes, 71, 72
Prins cyclization strategies
alkene geometry, 64, 65
allylic 1,2-diols in, 65
bryostatin 9, 69
diastereoselective nucleophilic
trapping, 62, 63
leucascandrolide A, 65–67
phorboxazole B, 70
potential pathways, 63, 64
(+)-SCH 351488, 67, 68
retrosynthetic approaches, 61, 62
430
Index
Carbon–carbon bonds cleavage, 177–182
Carbon–carbon double bond, metathesis
applications, 323–344
discovery and development, 323
eight-membered oxacycles synthesis
benzooxocin ring system, 331
Brevetoxin A, 334
Claisen–Ireland rearrangement, 330
conformational reorganization, 328
CTX3C synthesis, 334
enantioselective total synthesis,
331, 332
gauche effect, 326
heliannuols, benzooxocin core,
331, 332
Laurencia oxacycles, 325
(+)-laurencin, 325
octalactins, 332, 333
(+)-prelaureatin, 327, 328
RCM, protecting groups, 327, 328
relative stereochemistry, 329, 330
solandelactones, cyclopropyl lactone,
333, 334
tributylstannyl group, 329, 330
Grubbs catalyst, 325
metathesis catalysts examples, 323, 324
nine-membered oxacycles synthesis
eleutherobin, B-ring, 336, 337
formation, 335, 336
gambieric acids, 340
(–)-halicholacton, 338
halicholactone, 337
isolaurallene synthesis, 335, 336
(+)-obtusenyne synthesis, 336, 337
oxoninoquinolones, 336, 338
polycyclic ether skeletons, 340, 341
relative stereochemistry effect,
339, 340
topsentolide B 3 , stereoselective
synthesis, 338, 339
olefin metathesis, 323
ten-membered oxacycles synthesis
C1–C7 fragment synthesis, 341, 342
description, 341
microcarpalide synthesis, 342
olefin geometry, catalyst effect,
343–344
Carbon–carbon single bond formation
anion alkylation, 347–349
anionic cyclization, 298–300
cycloaddition and pericyclic reaction,
349–350
electrophilic cyclization, 295–298
free radical cyclization, 344–346
metal-induced cyclization, 300–306
metal-mediated cyclization, 346–347
photochemical processes, 310–311
Prins-type reaction cyclization, 350–351
radical reactions, 307–310
thermal cycloadditions and rearrangements,
306–307
Carbon–oxygen single bond formation
enamide halo-etherification, 352
epoxides ring opening, 291–292
hydroxy ketones and thioketals, 351–352
hydroxyl allene, intramolecular
cyclization, 353
hydroxyl ketones, reductive cyclization,
292–293
metal-mediated heterocyclization, 353–354
oxa-Michael reactions, 294–295
oxygenated nucleophiles, 288–291
pericyclic reaction, 355
polyenes oxidation, 291–292
Ullmann coupling, 293, 294
Carbonylation, lactones, 129–130
Carboxylation, lactones, 130–131
Carotenoid pigment, 158–159
C2–C3 THP-forming processes
Panek [4+2]-annulation strategies
2,6-cis DHP, 74
leucascandrolide A, 74, 75
(+)-SCH 351448, 75
stereoselective annulation method,
73, 74
Petasis–Ferrier union/rearrangement
mechanism of, 71
phorboxazole A, 72
spongistatin 1, 73
trisubstituted alkenes, 71, 72
Prins cyclization strategies
alkene geometry, 64, 65
allylic 1,2-diols in, 65
bryostatin 9, 69
diastereoselective nucleophilic
trapping, 62, 63
leucascandrolide A, 65–67
phorboxazole B, 70
potential pathways, 63, 64
(+)-SCH 351488, 67, 68
retrosynthetic approaches, 61, 62
430
Index