Palladium(II)-Catalyzed Direct ortho-C-H Acylation of Anilides by Oxidative Cross-Coupling with Aldehydes using tert-Butyl Hydroperoxide as Oxidant

被引:128
作者
Chan, Chun-Wo [1 ]
Zhou, Zhongyuan [1 ]
Yu, Wing-Yiu [1 ]
机构
[1] Hong Kong Polytech Univ, State Key Lab Chirosci, Dept Appl Biol & Chem Technol, Kowloon, Hong Kong, Peoples R China
关键词
acylation; 2-aminobenzophenones; C?H activation; Friedel-Crafts reaction; palladium; BOND FORMATION; STEREOSELECTIVE-SYNTHESIS; RADICAL REACTIONS; SUGASAWA REACTION; ORTHO-ARYLATION; O BOND; PD; CHEMISTRY; ARENES; SP(2);
D O I
10.1002/adsc.201100472
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
An efficient palladium-catalyzed C?H acylation with aldehydes using tert-butyl hydroperoxide (TBHP) transforms various anilides into synthetically useful 2-aminobenzophenone derivatives under mild conditions (40?degrees C, 3 h). The acylation reaction exhibits excellent regioselectivity and functional group tolerance, and simple aromatic aldehydes, functionalized aliphatic aldehydes and heteroaromatic aldehydes are effective coupling partners. The acylation reaction is probably initiated by a rate-limiting electrophilic C?H cyclopalladation (kH/kD=3.6; ?+=-0.74) to form an arylpalladium complex, followed by acyl radical functionalization.
引用
收藏
页码:2999 / 3006
页数:8
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