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铂(II)对烯烃的亲电活化:远不止是钯(II)的慢速版本。

Electrophilic activation of alkenes by platinum(II): so much more than a slow version of palladium(II).

作者信息

Chianese Anthony R, Lee Stephen J, Gagné Michel R

机构信息

Department of Chemistry, Colgate University, 13 Oak Drive, Hamilton, NY 13346, USA.

出版信息

Angew Chem Int Ed Engl. 2007;46(22):4042-59. doi: 10.1002/anie.200603954.

Abstract

The electrophilic activation of alkenes by transition-metal catalysts is a fundamental step in a rapidly growing number of catalytic processes. Although palladium is the best known metal for this purpose, the special properties of its third-row cousin platinum (strong metal-ligand bonds and slow substitution kinetics) have enabled the development of transformations that are initiated by addition to the C=C bonds by protic carbon, nitrogen, oxygen, and phosphorus nucleophiles, as well as alkene or arene nucleophiles. Additionally, reactivity profiles, which are often unique to platinum, provide wholly new reaction products. This Review concerns platinum-catalyzed electrophilic alkene activation reactions, with a special emphasis on the mechanistic properties of known systems, on the differences between platinum and palladium catalysts, and on the prospects for the development of new systems.

摘要

过渡金属催化剂对烯烃的亲电活化是越来越多催化过程中的一个基本步骤。尽管钯是最广为人知用于此目的的金属,但其第三周期同族元素铂的特殊性质(强金属-配体键和缓慢的取代动力学)使得质子性碳、氮、氧和磷亲核试剂以及烯烃或芳烃亲核试剂通过加成到C=C键引发的转化得以发展。此外,铂常常独有的反应活性特征能提供全新的反应产物。本综述关注铂催化的亲电烯烃活化反应,特别强调已知体系的机理性质、铂和钯催化剂之间的差异以及新体系开发的前景。

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