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催化烯丙基化反应中的活性中间体;Mizoroki-Heck、氧化 Heck 和 Fujiwara-Moritani 反应的途径。

Reactive intermediates in catalytic alkenylation; pathways for Mizoroki-Heck, oxidative Heck and Fujiwara-Moritani reactions.

机构信息

Pakistan Atomic Energy Commission, P.O. Box 1114, Islamabad, Pakistan.

出版信息

Chem Commun (Camb). 2013 Oct 4;49(76):8430-40. doi: 10.1039/c3cc44842h.

DOI:10.1039/c3cc44842h
PMID:23949625
Abstract

Several closely related palladium-catalysed reactions involve the addition of Pd-C across an alkene, and subsequent β-elimination of Pd-H to give a more substituted alkene. The Pd-C precursor, normally possessing an sp(2) carbon bound to palladium, can be formed in several different ways, leading to sub-classes of reaction based on a common principle and convergent outcomes. The reaction pathway can vary from simple to highly subtle depending on the nature of the reactants and the ligation of the catalyst. Mechanistic analysis provides results that elucidate the pathway and link the different reaction types. The identification of reactive intermediates by NMR, ES-MS and other spectroscopic techniques, or by less direct methods, is an integral part of the process. This Feature Article covers ligand-free palladium catalysis, including the contributions of the authors, and separates catalysis where ligands are involved into cationic and neutral pathways.

摘要

几种密切相关的钯催化反应涉及 Pd-C 在烯烃上的加成,以及随后的 Pd-H 的 β-消除,从而得到取代程度更高的烯烃。Pd-C 前体通常具有一个与钯键合的 sp(2) 碳原子,可以通过几种不同的方式形成,从而根据共同的原理和收敛的结果形成反应的子类。反应途径可以根据反应物的性质和催化剂的配位而从简单到高度复杂变化。机理分析提供了阐明途径并将不同反应类型联系起来的结果。通过 NMR、ES-MS 和其他光谱技术或通过间接方法鉴定反应中间体是该过程的一个组成部分。这篇专题文章涵盖了无配体钯催化,包括作者的贡献,并将涉及配体的催化分为阳离子和中性途径。

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