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手性催化剂在不对称羰基ene反应中的应用

张永丽, 张瑞, 常宏宏, 魏文珑*, 李兴*

化学进展 ›› 2014, Vol. 26 ›› Issue (09) :1492-1505

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化学进展 ›› 2014, Vol. 26 ›› Issue (09) :1492-1505 DOI: 10.7536/PC140319
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手性催化剂在不对称羰基ene反应中的应用

    张永丽, 张瑞, 常宏宏, 魏文珑*, 李兴*
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Asymmetric Carbonyl-ene Reactions Promoted by Chiral Catalysts

  • Zhang Yongli, Zhang Rui, Chang Honghong, Wei Wenlong*, Li Xing*
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摘要

手性高烯丙基醇类化合物是一类非常重要的有机合成中间体,被广泛应用于药物分子和天然产物的合成中,不对称羰基ene反应是构建此类化合物最有效的方法之一,近年来已经取得了巨大进展。目前,在不对称羰基ene反应中的手性催化剂主要有如Mg、Ca、Sc、Ti、Co、Ni、Cu、Rh、Pd、Pt等金属与手性配体络合形成的配合物,以及一些手性有机小分子,大部分都取得了较好的催化活性与对映选择性。本文就此评述了各类手性催化剂在不对称羰基ene反应中的应用,不对称诱导反应的机理,以及催化剂分子结构及反应条件对催化活性和对映选择性的影响。

Abstract

Chiral homoallylic alcohols are important drug intermediates for synthesis of pharmaceutical molecules and nature products. Asymmetric carbonyl-ene reaction is a powerful tool for the preparation of them. The chiral catalysts reported include chiral organometallic complexs and chiral organic molecules, which have achieved good catalytic activity and enantioselectivity. This paper reviews the application of various types of chiral catalysts in asymmetric carbonyl-ene reactions, the reaction mechanism of asymmetric induction, the effect of the structure of the catalysts and reaction conditions on the catalytic activity and enantioselectivity.

Contents
1 Introduction
2 Application of chiral organometallic catalysts in carbonyl-ene reaction
2.1 Chiral alkaline earth metal catalyst
2.2 Chiral transition metal catalyst
2.3 Chiral indium catalyst
3 Chiral organocatalyst
3.1 Chiral phosphorus amide
3.2 Chiral binaphthol and its derivatives
4 Conclusion and outlook

Graphical abstract

关键词

手性高烯丙醇 / 羰基ene反应 / 不对称催化 / 手性有机金属催化剂 / 手性有机小分子催化剂

Key words

homoallylic alcohols / carbonyl-ene / asymmetric catalysis / chiral organometallic catalysts / chiral organic molecular catalysts

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引用格式 ▾
张永丽, 张瑞, 常宏宏, 魏文珑, 李兴. 手性催化剂在不对称羰基ene反应中的应用[J]. 化学进展, 2014, 26(09): 1492-1505 DOI:10.7536/PC140319
Zhang Yongli, Zhang Rui, Chang Honghong, Wei Wenlong, Li Xing. Asymmetric Carbonyl-ene Reactions Promoted by Chiral Catalysts[J]. Progress in Chemistry, 2014, 26(09): 1492-1505 DOI:10.7536/PC140319

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