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

167 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
Externally publishedYes

Fingerprint

Cyclization
Dimethyl Sulfoxide
Oxidants
Ethylene Dichlorides
Copper
Lactams
Atmosphere
Catalysts
Dimethyl sulfoxide
Substrates
Isotopes
Silver
Chemical activation
Oxidation
Kinetics
2-oxindole
cupric chloride

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

Copper-catalyzed intramolecular C(sp3)-H and C(sp2)-H amidation by oxidative cyclization. / Wang, Zhen; Ni, Jizhi; Kuninobu, Yoichiro; Kanai, Motomu.

In: Angewandte Chemie - International Edition, Vol. 53, No. 13, 24.03.2014, p. 3496-3499.

Research output: Contribution to journalArticle

@article{6cb1d3372224450bbec02b0f24e76853,
title = "Copper-catalyzed intramolecular C(sp3)-H and C(sp2)-H amidation by oxidative cyclization",
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.",
author = "Zhen Wang and Jizhi Ni and Yoichiro Kuninobu and Motomu Kanai",
year = "2014",
month = "3",
day = "24",
doi = "10.1002/anie.201311105",
language = "English",
volume = "53",
pages = "3496--3499",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "13",

}

TY - JOUR

T1 - Copper-catalyzed intramolecular C(sp3)-H and C(sp2)-H amidation by oxidative cyclization

AU - Wang, Zhen

AU - Ni, Jizhi

AU - Kuninobu, Yoichiro

AU - Kanai, Motomu

PY - 2014/3/24

Y1 - 2014/3/24

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84896441672&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84896441672&partnerID=8YFLogxK

U2 - 10.1002/anie.201311105

DO - 10.1002/anie.201311105

M3 - Article

C2 - 24616043

AN - SCOPUS:84896441672

VL - 53

SP - 3496

EP - 3499

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 13

ER -