First comprehensive bakkane approach: stereoselective and efficient dichloroketene-based total syntheses of (+/-)- and (-)-9-acetoxyfukinanolide, (+/-)- and (+)-bakkenolide A, (-)-bakkenolides III, B, C, H, L, V, and X, (+/-)- and (-)-homogynolide A, (+/-)-homogynolide B, and (+/-)-palmosalide C.
Cycloaddition of dichloroketene with dimethylcyclohexenes has been used as the key reaction in an efficient, general approach to the bakkanes. New methods and methodologies that have been developed in this work include spiro beta-methylene-gamma-butyrolactonizations, a vicinal dicarboxylation, an angelic ester preparation, a transesterification, an epoxy ketone double reduction, and a retro aldol-aldol approach to low-energy aldol isomers.
Brocksom
Timothy J
TJ
Chimie Recherche (LEDSS), Université Joseph Fourier, BP 53X, 38041 Grenoble, France.
Coelho
Fernando
F
Deprés
Jean-Pierre
JP
Greene
Andrew E
AE
Freire De Lima
Marco E
ME
Hamelin
Olivier
O
Hartmann
Benoît
B
Kanazawa
Alice M
AM
Wang
Yanyun
Y
D015107:4-Butyrolactone / Q000031:analogs & derivatives* / Q000138:chemical synthesis*; D003510:Cyclohexanes / Q000737:chemistry; D053138:Cyclohexenes; D004000:Dichloroethylenes / Q000737:chemistry*; D036901:Petasites / Q000737:chemistry; D012717:Sesquiterpenes / Q000138:chemical synthesis*; D013237:Stereoisomerism
D003510:Cyclohexanes; D053138:Cyclohexenes; D004000:Dichloroethylenes; D012717:Sesquiterpenes; C052568:cyclohexene; C039586:dichloroketene; D015107:4-Butyrolactone; C016257:bakkenolide A