Copper-catalyzed intramolecular C(sp3)-H and C(sp2)-H amidation by oxidative cyclization

Zhen Wang, Jizhi Ni, Yoichiro Kuninobu, Motomu Kanai

Research output: Contribution to journalArticle

176 Citations (Scopus)

Abstract

The first copper-catalyzed intramolecular C(sp3)-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(sp3)-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 β-lactams were obtained in excellent yield, even on gram scale. Use of CuCl2 and Ag2CO3 under an O2 atmosphere in dimethyl sulfoxide, however, leads to 2-indolinone selectively by C(sp2)-H amidation. Kinetic isotope effect (KIE) studies indicated that C-H bond activation is the rate-determining step. The 5-methoxyquinolyl directing group could be removed by oxidation. Silver ox: By using a Cu(OAc)2 catalyst and an Ag2CO3 oxidant in dichloroethane solvent, C(sp3)-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 β-lactams were obtained in excellent yield, even on a gram scale. Use of CuCl2 and Ag2CO3 under an O2 atmosphere led to 2-indolinone selectively synthesized by C(sp2)-H amidation. DMSO=dimethylsulfoxide.

Original languageEnglish
Pages (from-to)3496-3499
Number of pages4
JournalAngewandte Chemie - International Edition
Volume53
Issue number13
DOIs
Publication statusPublished - Mar 24 2014

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Fingerprint Dive into the research topics of 'Copper-catalyzed intramolecular C(sp<sup>3</sup>)-H and C(sp<sup>2</sup>)-H amidation by oxidative cyclization'. Together they form a unique fingerprint.

  • Cite this