Copper-Catalyzed Trifluoromethylation-Initiated Radical 1,2-Aryl Migration in ,-Diaryl Allylic Alcohols

被引：276

作者：

Liu, Xiaowu ^{[1
]}

Xiong, Fei ^{[1
]}

Huang, Xuanping ^{[1
]}

Xu, Liang ^{[2
]}

Li, Pengfei ^{[2
]}

Wu, Xiaoxing ^{[1
]}

机构：

[1] Chinese Acad Sci, Guangzhou Inst Biomed & Hlth, Guangzhou 510530, Guangdong, Peoples R China

[2] Xi An Jiao Tong Univ, Ctr Organ Chem, Frontier Inst Sci & Technol FIST, Xian 710054, Shaanxi, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2013年 / 52卷 / 27期

基金：

美国国家科学基金会;

关键词：

copper; migration; radical reactions; rearrangement; trifluoromethylation; ENANTIOSELECTIVE ALPHA-TRIFLUOROMETHYLATION; PD(II)-CATALYZED ORTHO-TRIFLUOROMETHYLATION; NUCLEOPHILIC TRIFLUOROMETHYLATION; MEDIATED TRIFLUOROMETHYLATION; ELECTROPHILIC TRIFLUOROMETHYLATION; OXIDATIVE TRIFLUOROMETHYLATION; CARBONYL-COMPOUNDS; IPSO-SUBSTITUTION; ROOM-TEMPERATURE; BORONIC ACIDS;

D O I：

10.1002/anie.201302673

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Not only symmetrical, but also unsymmetrical α,α-diaryl allylic alcohols are employed as substrates in the title reaction. A number of arenes and even heteroarenes underwent radical 1,2-aryl migration ("neophyl rearrangement") to produce α-aryl β-trifluoromethyl ketones. The preferential migration of electron-deficient aryl groups over electron-rich ones in unsymmetrical substrates supports the radical mechanism, which was further confirmed by DFT calculations. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：6962 / 6966

页数：5

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