Catalytic asymmetric epoxidation of α,β-unsaturated carboxylic acid imidazolides and amides by lanthanide-BINOL complexes

被引：33

作者：

Ohshima, T ^{[1
]}

Nemoto, T ^{[1
]}

Tosaki, S ^{[1
]}

Kakei, H ^{[1
]}

Gnanadesikan, V ^{[1
]}

Shibasaki, M ^{[1
]}

机构：

[1] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, Tokyo 1130033, Japan

来源：

TETRAHEDRON | 2003年 / 59卷 / 52期

基金：

日本学术振兴会;

关键词：

asymmetric catalysis; epoxidation; lanthanide; molecular orbital calculation;

D O I：

10.1016/j.tet.2003.06.010

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Highly enantioselective catalytic asymmetric epoxidation of alpha,beta-unsaturated carboxylic acid imidazolides and simple amides was developed. In the presence of 5-10 mol% of lanthanide-BINOL complexes, the reaction proceeded smoothly with high substrate generality. In particular, in the cases of alpha,beta-tinsaturated amides, there was nearly perfect enantioselectivity ( > 99% ee). The corresponding epoxides were successfully transformed into many types of useful chiral compounds such as alpha,beta-epoxy esters, alpha,beta-epoxy amides, alpha,beta-epoxy aldehydes, alpha,beta-epoxy beta-keto ester, and alpha- and beta-hydroxy carbonyl compounds. B3LYP density functional studies were performed to predict substrate reactivity. (C) 2003 Elsevier Ltd. All rights reserved.

引用

页码：10485 / 10497

页数：13

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