Construction of the benzylic quaternary carbon center of zoanthenol by intramolecular Mizoroki-Heck reaction of enone.
[reaction: see text]. Stereocontrolled synthesis of the ABC ring framework of zoanthenol has been achieved. Our studies show that a beta,beta-disubstituted enone can act as a good acceptor of arylpalladium intermediates in the formation of a congested benzylic quaternary carbon center through an intramoleculer Mizoroki-Heck reaction. The cis B/C ring system was stereoselectively converted to the trans-fused framework through a SmI2-promoted deoxygenation of the alpha-hydroxy ketone.
Hirai
Go
G
Department of Chemistry, Graduate School of Science, Tohoku University, and CREST, Japan Science and Technology Corporation (JST), Sendai 980-8578, Japan.
Koizumi
Yuuki
Y
Moharram
Sameh M
SM
Oguri
Hiroki
H
Hirama
Masahiro
M
D000470:Alkaloids / Q000737:chemistry; D001952:Bridged-Ring Compounds / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006572:Heterocyclic Compounds, Bridged-Ring / Q000737:chemistry*; D007202:Indicators and Reagents; D008968:Molecular Conformation; D010165:Palladium / Q000737:chemistry
D000470:Alkaloids; D001952:Bridged-Ring Compounds; D006572:Heterocyclic Compounds, Bridged-Ring; D007202:Indicators and Reagents; C457061:zoanthenol; D010165:Palladium