Highlights of the Rh-catalysed asymmetric hydroformylation of alkenes using phosphorus donor ligands
Highlights of the Rh-catalysed asymmetric hydroformylation of alkenes using phosphorus donor ligands
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DOI：
10.1016/j.tetasy.2010.05.037
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发表时间：
2010-05-17
影响因子：
--
通讯作者：
Claver, Carmen
中科院分区：
文献类型：
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作者：
Gual, Aitor;Godard, Cyril;Claver, Carmen
烯烃底物的种类相对较多。对催化循环的不同步骤的阐明和静止状态的表征，以及能够提供高对映体选择性的几种类型的配体的发现，使得铑催化的氢化物成为合成有用的工具。多年来，含有亚磷酸酯部分的配体如二亚磷酸酯和膦-亚磷酸酯被认为是在该过程中实现高对映选择性的最成功的配体。事实上，亚磷酸酯膦BINAPHOS 43及其衍生物即使在今天也是选择性和范围方面最成功的配体。然而，最近显示二膦衍生物提供高水平的选择性。因此可以得出结论，实现高的对映选择性的关键不是参与与金属配位的磷官能团的类型，而是配位配体的特定空间排列。(C)2010爱思唯尔有限公司版权所有。
relatively high variety of alkene substrates. The elucidation of the different steps of the catalytic cycle and the characterisation of the resting state, together with the discovery of several types of ligands that are able to provide high enantioselectivities, have made the rhodium-catalysed hydroformylation a synthetically useful tool. For years, ligands containing phosphite moieties such as diphosphites and phosphine-phosphites were considered the most successful ligands to achieve high enantioselectivies in this process. In fact, the phosphite-phosphine BINAPHOS 43 and its derivatives are even today the most successful ligands in terms of selectivity and scope. Recently however, diphosphine derivatives were shown to provide high levels of selectivity. It can consequently be concluded that the key to achieve high enantioselectivities is not the type the phosphorus function involved in the coordination to the metal, but the particular spatial arrangement of the coordinated ligand. (C) 2010 Elsevier Ltd. All rights reserved.