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芳酰胺与未活化烯烃的螯合辅助氧化偶联反应:亲电钌氢化物催化剂促进乙烯基C-H键活化的机理证据

Chelate-Assisted Oxidative Coupling Reaction of Arylamides and Unactivated Alkenes: Mechanistic Evidence for Vinyl C-H Bond Activation Promoted by an Electrophilic Ruthenium-Hydride Catalyst.

作者信息

Kwon Ki-Hyeok, Lee Do W, Yi Chae S

机构信息

Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201-1881.

出版信息

Organometallics. 2010 Oct 21;29(22):5748-5750. doi: 10.1021/om100764c.

Abstract

The cationic ruthenium-hydride complex (η(6)-C(6)H(6))(PCy(3))(CO)RuHBF(4) (-) was found to be a highly regioselective catalyst for the oxidative C-H coupling reaction of aryl-substituted amides and unactivated alkenes to give ortho-alkenylamide products. The kinetic and spectroscopic analyses support a mechanism involving a rapid vinyl C-H activation followed by a rate-limiting C-C bond formation steps.

摘要

阳离子氢化钌配合物(η(6)-C(6)H(6))(PCy(3))(CO)RuHBF(4) (-)被发现是芳基取代酰胺与未活化烯烃的氧化C-H偶联反应生成邻烯基酰胺产物的高区域选择性催化剂。动力学和光谱分析支持一种机制,该机制涉及快速的乙烯基C-H活化,随后是限速的C-C键形成步骤。

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