Construction of the benzylic quaternary carbon center of zoanthenol by intramolecular Mizoroki-Heck reaction of enone

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 Sml(2)-promoted deoxygenation of the alpha-hydroxy ketone.