N-Heterocyclic carbene-catalyzed remote C(sp3)–H acylation of amides

[Display omitted] An N-heterocyclic carbene catalyzed benzylic C–H acylation of o-alkyl benzamides and cascade cyclization is developed through a radical-mediated 1,5-hydrogen atom transfer (HAT) mechanism. Different from photoredox catalysis, this light-free approach enables the generation of amidy...

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Bibliographic Details
Published inTetrahedron letters Vol. 121; pp. 154483 - 154486
Main Authors Xu, Huiwei, Mo, Jia-Nan, Liu, Wen-Deng, Zhao, Jiannan
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 17.05.2023
Elsevier
Subjects
Acylation
Chemistry
Chemistry, Organic
C–H functionalization
Hydrogen atom transfer
NHC organocatalysis
Physical Sciences
Radicals
Science & Technology
NHC organocatalysis
Hydrogen atom transfer
C–H functionalization
Radicals
Acylation
ACTIVE ALDEHYDES
PHOTOREDOX
ELECTRON-TRANSFER PROPERTIES
ALKYLATION
LIGHT
ORGANOCATALYSIS
C-H functionalization
MOLECULES
FUNCTIONALIZATION
AMINATION
OXIDATIONS
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Summary:[Display omitted] An N-heterocyclic carbene catalyzed benzylic C–H acylation of o-alkyl benzamides and cascade cyclization is developed through a radical-mediated 1,5-hydrogen atom transfer (HAT) mechanism. Different from photoredox catalysis, this light-free approach enables the generation of amidyl radicals through single-electron transfer (SET) with Breslow enolates. The mild process tolerates most common functional groups and delivers a variety of dihydroisoquinolinones in moderate to high yields. The electrochemical character of the aryloxyamide is consistent with the hypothesis of ground-state SET and a plausible mechanism for the organocatalytic transformation is proposed.
ISSN:0040-4039
1873-3581
DOI:10.1016/j.tetlet.2023.154483