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.

引用

页码：6873 / 6876

页数：4

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