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铱催化烯丙基取代反应中的亚磷酰胺配体

Phosphoramidite ligands in iridium-catalyzed allylic substitution.

作者信息

Polet Damien, Alexakis Alexandre, Tissot-Croset Karine, Corminboeuf Clémence, Ditrich Klaus

机构信息

Department of Organic Chemistry, University of Geneva, 30, quai Ernest Ansermet, 1211 Geneva 4, Switzerland.

出版信息

Chemistry. 2006 Apr 24;12(13):3596-609. doi: 10.1002/chem.200501180.

DOI:10.1002/chem.200501180
PMID:16453353
Abstract

A new phosphoramidite ligand was used in the iridium-catalyzed allylic substitution reaction. This permitted high regio- and enantioselectivities on a wide variety of substrates and nucleophiles. Because of the stereospecificity of the reaction obtained by using branched substrates, a kinetic resolution reaction was attempted. The origin of the impressive efficiency of this ligand in terms of kinetics was explored in detail, as was the role of the substituent in the ortho-position of the amine moiety.

摘要

一种新型亚磷酰胺配体被用于铱催化的烯丙基取代反应。这使得在多种底物和亲核试剂上都能实现高区域选择性和对映选择性。由于使用支链底物获得的反应的立体专一性,尝试了动力学拆分反应。详细探究了该配体在动力学方面令人印象深刻的效率的来源,以及胺部分邻位取代基的作用。

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