Copper-Catalyzed Intramolecular C(sp3)-H and C(sp2)-H Amidation by Oxidative Cyclization

被引：204
|
作者：
Wang, Zhen [1 ]
Ni, Jizhi [1 ]
Kuninobu, Yoichiro [1 ,2 ]
Kanai, Motomu [1 ,2 ]
机构：
[1] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, Tokyo 1130033, Japan
[2] ERATO Japan Sci & Technol Agcy JST, Kanai Life Sci Catalysis Project, Tokyo 1130033, Japan
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 13期
关键词：
CH activation; copper; cyclization; heterocycles; lactams; BETA-AMINO ACIDS; N BOND FORMATION; C(SP(3))-H BONDS; STEREOSELECTIVE-SYNTHESIS; BECKMANN REARRANGEMENT; ACTIVATION REACTIONS; C(SP(2))-H BONDS; LACTAM FORMATION; SINGLE-ELECTRON; ALKYL AZIDES;
D O I：
10.1002/anie.201311105
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The first copper-catalyzed intramolecular C(sp(3))H and C(sp(2))H oxidative amidation has been developed. Using a Cu(OAc)(2) catalyst and an Ag2CO3 oxidant in dichloroethane solvent, C(sp(3))H amidation proceeded at a terminal methyl group, as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various -lactams were obtained in excellent yield, even on gram scale. Use of CuCl2 and Ag2CO3 under an O-2 atmosphere in dimethyl sulfoxide, however, leads to 2-indolinone selectively by C(sp(2))H amidation. Kinetic isotope effect (KIE) studies indicated that CH bond activation is the rate-determining step. The 5-methoxyquinolyl directing group could be removed by oxidation.
引用
收藏
页码：3496 / 3499
页数：4
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