Mechanistic Understanding of the Unexpected Meta Selectivity in Copper-Catalyzed Anilide C-H Bond Arylation

被引：191

作者：

Chen, Bo ^{[2
]}

Hou, Xue-Long ^{[1
,2
]}

Li, Yu-Xue ^{[1
]}

Wu, Yun-Dong ^{[2
,3
]}

机构：

[1] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China

[2] Chinese Acad Sci, Shanghai Inst Organ Chem, Shanghai Hong Kong Joint Lab Chem Synth, Shanghai 200032, Peoples R China

[3] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 20期

关键词：

PROTON-ABSTRACTION MECHANISM; INTRAMOLECULAR ARYLATION; COUPLING REACTIONS; ACTIVATION; ARENES; ARYL; FUNCTIONALIZATION; BORYLATION; CLEAVAGE; LIGANDS;

D O I：

10.1021/ja201425e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

DFT calculations suggest that the unexpected meta product in the copper-catalyzed arylation of anilide is formed via a Heck-like four-membered-ring transition state involving a Cu(III)-Ph species. A competitive electrophilic substitution mechanism delivers the ortho product when a methoxy group is present at the meta position of pivanilide. A series of experiments including kinetic studies support the involvement of a Cu(I) catalyst.

引用

页码：7668 / 7671

页数：4

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