Rhodium(I)-Catalyzed Highly Enantioselective Insertion of Carbenoid into Si-H: Efficient Access to Functional Chiral Silanes

被引：152

作者：

Chen, Diao ^{[1
]}

Zhu, Dong-Xing ^{[1
]}

Xu, Ming-Hua ^{[1
]}

机构：

[1] Chinese Acad Sci, Shanghai Inst Mat Med, State Key Lab Drug Res, 555 Zuchongzhi Rd, Shanghai 201203, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2016年 / 138卷 / 05期

基金：

中国国家自然科学基金;

关键词：

CATALYZED ASYMMETRIC ARYLATION; CONJUGATE SILYL TRANSFER; DIRHODIUM(II) CARBOXYLATES; SULFUR-OLEFINS; SILICON; LIGANDS; BOND; CARBON; ACIDS; IDENTIFICATION;

D O I：

10.1021/jacs.5b12960

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The first rhodium(I)-catalyzed enantioselective Si-H insertion reaction of alpha-diazoesters and alpha-diazophosphonates has been developed. The use of a C-1-symmetric chiral diene ligand enabled the asymmetric reaction to proceed under exceptionally mild conditions and give versatile chiral a-silyl esters and phosphonates with excellent enantioselectivities (up to 99% ee). The mechanism and stereothemical pathway of this novel Rh(I)-carbene-directed Si-H insertion was investigated by deuterium kinetic isotope effect experiments and DFT calculations.

引用

页码：1498 / 1501

页数：4

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