Enantioselective cyanosilylation of ketones catalyzed by double-activation catalysts with N-oxides

被引：51

作者：

Chen, FX

Qin, B

Feng, XM ^{[1
]}

Zhang, GL

Jiang, YZ

机构：

[1] Sichuan Univ, Minist Educ, Coll Chem, Key Lab Green Chem & Technol, Chengdu 610064, Peoples R China

[2] Chinese Acad Sci, Chengdu Inst Biol, Chengdu 610041, Peoples R China

[3] Chinese Acad Sci, Chengdu Inst Organ Chem, Chengdu 610041, Peoples R China

来源：

TETRAHEDRON | 2004年 / 60卷 / 46期

基金：

中国国家自然科学基金; 中国博士后科学基金;

关键词：

asymmetric catalysis; cyanohydrin; cyanosilylation; double-activation; ketone; N-oxide;

D O I：

10.1016/j.tet.2004.06.133

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Enantioselective addition of trimethylsilyl cyanide to ketones by a catalytic double-activation method is described. By combinatorially using 2.0 mol% of a chiral salen-titanium complex and 1.0 mol% of an achiral tertiary amine N-oxide, aromatic, aliphatic and alpha,beta-unsaturated ketones are converted into corresponding cyanohydrin trimethylsilyl ethers with 50-93% yield and 59-86% ee. The effects of ligand structure, catalyst loading and substrate concentration, solvents, the nature of Lewis base, counter ion and other additives, temperature, and substrate structure on the enantioselectivity are discussed. Three possible paths to achieve the asymmetric version of double-activation catalysis and two independent examples of it are proposed. (C) 2004 Elsevier Ltd. All rights reserved.

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收藏

页码：10449 / 10460

页数：12

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