铜（I）催化的格氏试剂对α-甲基取代的α,β-不饱和酮的不对称 1,2-加成。

Copper(I) catalyzed asymmetric 1,2-addition of Grignard reagents to α-methyl substituted α,β-unsaturated ketones.

机构信息

Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.

出版信息

Chem Commun (Camb). 2012 Feb 1;48(10):1478-80. doi: 10.1039/c1cc16725a. Epub 2011 Nov 28.

Abstract

The first catalytic enantioselective 1,2-addition of Grignard reagents to ketones is presented. This additive-free copper(I) catalyzed 1,2-addition provides chiral allylic tertiary alcohols with an er of up to 98:2 and excellent yields due to the complete shift of overwhelming 1,4-selectivity of copper(I)-catalysts towards 1,2-selectivity in the addition reaction to enones.

摘要

首次报道了格氏试剂对酮的催化对映选择性 1,2-加成反应。这种无添加剂的铜（I）催化的 1,2-加成反应提供了手性烯丙基叔醇，ee 值高达 98:2，产率优异，这是由于铜（I）催化剂在对烯酮加成反应中，从压倒性的 1,4-选择性完全转变为 1,2-选择性。