Hirai Go, Koizumi Yuuki, Moharram Sameh M, Oguri Hiroki, Hirama Masahiro
Department of Chemistry, Graduate School of Science, Tohoku University, and CREST, Japan Science and Technology Corporation (JST), Sendai 980-8578, Japan.
Org Lett. 2002 May 2;4(9):1627-30. doi: 10.1021/ol025852d.
[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.
[反应：见正文]。已经实现了zoanthenol的ABC环骨架的立体控制合成。我们的研究表明，β，β-二取代烯酮在通过分子内Mizoroki-Heck反应形成拥挤的苄基季碳中心时，可以作为芳基钯中间体的良好受体。通过SmI₂促进的α-羟基酮脱氧反应，顺式B/C环系统被立体选择性地转化为反式稠合骨架。
