Asymmetric Induction at Remote Quaternary Centers of Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation

被引：51
作者：
Naganawa, Yuki [1 ]
Kawagishi, Mayu [1 ]
Ito, Jun-ichi [1 ]
Nishiyama, Hisao [1 ]
机构：
[1] Nagoya Univ, Grad Sch Engn, Dept Appl Chem, Chikusa Ku, Nagoya, Aichi 4648603, Japan
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 24期
基金：
日本学术振兴会;
关键词：
asymmetric synthesis; desymmetrization; hydrosilylation; quaternary centers; rhodium; ENANTIOSELECTIVE CONSTRUCTION; NATURAL-PRODUCTS; FACILE SYNTHESIS; HECK ARYLATIONS; REDUCTION; DESYMMETRIZATION; ESTERS; TRANSFORMATIONS; STEREOCENTERS; BEARING;
D O I：
10.1002/anie.201601636
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The enantioselective desymmetrizing conjugate hydrosilylation of prochiral differently gamma, gamma-disubstituted cyclohexadienone derivatives 2 to furnish the corresponding cyclohexenones 4 with a remote chiral all-carbon quaternary center at the g position is described. Chiral rhodium-bis(oxazolinyl)-phenyl complexes 1 were effective catalysts for this transformation. This catalytic system was extended to the asymmetric transformation of spirocarbocyclic cyclohexadienones 5 to give the corresponding products 6 with high enantiomeric ratios.
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收藏
页码：6873 / 6876
页数：4
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