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

页码：3496 / 3499

页数：4

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