含手性磷中心的功能化膦的不对称合成及有机金属化学。

Asymmetric synthesis and organometallic chemistry of functionalized phosphines containing stereogenic phosphorus centers.

作者信息

Leung Pak-Hing

机构信息

Department of Chemistry, National University of Singapore, Kent Ridge, Singapore 119260.

出版信息

Acc Chem Res. 2004 Mar;37(3):169-77. doi: 10.1021/ar030008o.

DOI:10.1021/ar030008o

PMID:15023084

Abstract

A series of organometallic reagents containing orthometalated chiral amine auxiliaries have been utilized as chiral templates to activate phospholes, vinylphosphines, and alkynylphosphines toward asymmetric ligand transformations via cycloaddition and hydroamination reactions. By a systemic manipulation of the subtle stereoelectronic properties of the auxiliaries and the metal centers, the template properties could be modified and the origins of stereoselectivity revealed. The chiral templates are able to control the disposition of selected functionalities into designated locations on the transformed P-stereogenic mono- and diphosphine ligands. This Account provides an overview of our recent work in this area.

摘要

一系列含有邻位金属化手性胺辅助剂的有机金属试剂已被用作手性模板，以通过环加成和氢胺化反应激活膦、乙烯基膦和炔基膦，实现不对称配体转化。通过对辅助剂和金属中心的微妙立体电子性质进行系统调控，可以改变模板性质并揭示立体选择性的起源。这些手性模板能够将选定的官能团定向排布到转化后的P-立体中心单膦和双膦配体的指定位置。本综述介绍了我们近期在该领域的工作。