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手性膦-亚磷酸酯配体的特征及其在不对称催化中的应用

Features and Application in Asymmetric Catalysis of Chiral Phosphine-Phosphite Ligands.

作者信息

Pizzano Antonio

机构信息

Instituto de Investigaciones Químicas (IIQ), and Centro de Innovación en Química Avanzada (ORFEO-CINQA), CSIC and Universidad de Sevilla, Américo Vespucio 49, 41092, Seville, Spain.

出版信息

Chem Rec. 2016 Dec;16(6):2595-2618. doi: 10.1002/tcr.201600076. Epub 2016 Aug 10.

DOI:10.1002/tcr.201600076
PMID:27506574
Abstract

Chiral phosphine-phosphites are a class of ligands for asymmetric catalysis characterized by two coordinating functionalities with different electronic properties. These ligands also possess a highly modular structure and, due to versatile synthetic processes, they can be tuned precisely in the catalyst optimization process. Research regarding the application of these ligands in several enantioselective catalytic processes has provided outstanding results in a good number of them. These processes include not only Rh catalyzed reactions, such as olefin hydrogenation and hydroformylation, but also other reactions, such as hydrogenation of olefins and imines by Ru complexes, of imines and N-heterocycles by Ir derivatives, allyl alkylation or conjugate addition by Cu catalysts, or hydrocyanation of olefins by Ni ones. Overall, the use of these ligands has led to the preparation of a wide variety of chiral building blocks with high enantiomeric excess. Therefore, phosphine-phosphites have become in an important class of ligands in asymmetric catalysis.

摘要

手性亚磷酸酯膦是一类用于不对称催化的配体,其特征在于具有两种具有不同电子性质的配位官能团。这些配体还具有高度模块化的结构,并且由于合成方法多样,在催化剂优化过程中可以对其进行精确调控。关于这些配体在多种对映选择性催化过程中的应用研究,在许多方面都取得了优异的成果。这些过程不仅包括铑催化的反应,如烯烃氢化和氢甲酰化反应,还包括其他反应,如钌配合物催化的烯烃和亚胺的氢化反应、铱衍生物催化的亚胺和氮杂环的氢化反应、铜催化剂催化的烯丙基烷基化或共轭加成反应,或镍催化剂催化的烯烃氢氰化反应。总体而言,这些配体的使用已导致制备出了大量具有高对映体过量的手性结构单元。因此,亚磷酸酯膦已成为不对称催化中一类重要的配体。

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