Approach to a new model of induction of stereoselectivity in the Nicholas reaction via a chiral 1-alkoxy-propargylium cation

被引：10

作者：

Montaña, AM ^{[1
]}

Cano, M ^{[1
]}

机构：

[1] Univ Barcelona, Dept Organ Chem, E-08028 Barcelona, Spain

来源：

TETRAHEDRON | 2002年 / 58卷 / 05期

关键词：

Nicholas reaction; syn-anti diastereoselectivity; enantioselectivity; cobalt complexes; enantiopure propargyl acetals;

D O I：

10.1016/S0040-4020(01)01188-7

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A systematic study on the syn-anti diastereoselectivity of the Nicholas reaction between enantiopure propargyl acetal dicobalt-hexacarbonyl complexes, as precursors of chiral propargyl cobalt-hexacarbonyl cations, and several linear and cyclic silyl enol ethers is presented. A high yield up to 95% and high syn-anti diastereoselectivity (from 85:15 up to > 99:1) is observed in the generation of the two new stereocenters. Moderate, but promising, syn(R,R)-syn(S,S), up to 70:30, is also observed in this preliminary work. This syn(R,R)syn(S,S) diastereoselectivity formally would correspond to the enantioselectivity of the Nicholas reaction once the chiral auxiliary should be removed, in order to be recycled. This is the first approach to the induction of 'enantioselectivity' in the Nicholas C-C coupling based on cheap and commercially available enantiopure alcohols as chiral auxiliaries. (C) 2002 Elsevier Science Ltd. All rights reserved.

引用

页码：933 / 951

页数：19

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