Iron-Catalyzed ortho C−H Arylation and Methylation of Pivalophenone N−H Imines

Wengang Xu; Naohiko Yoshikai

doi:10.1002/cssc.201900164

Iron-Catalyzed ortho C−H Arylation and Methylation of Pivalophenone N−H Imines

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Abstract

Iron-catalyzed ortho C−H arylation and methylation reactions of pivalophenone N−H imines are reported. The pivaloyl N−H imine proved an excellent directing group for the arylation with diarylzinc reagents in the presence of an iron-diphosphine catalyst and 2,3-dichlorobutane at room temperature. A similar catalytic system also allowed methylation with Me₃Al at 70 °C. The pivaloyl imine of the product could be readily converted to a cyano group, thus allowing convenient preparation of ortho-functionalized benzonitriles.

Original language	English
Pages (from-to)	3049-3053
Number of pages	5
Journal	ChemSusChem
Volume	12
Issue number	13
DOIs	https://doi.org/10.1002/cssc.201900164
Publication status	Published - 2019 Jul 5
Externally published	Yes

Keywords

arylation
C−H activation
iron
methylation
organometallic reagents

ASJC Scopus subject areas

Environmental Chemistry
Chemical Engineering(all)
Materials Science(all)
Energy(all)

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title = "Iron-Catalyzed ortho C−H Arylation and Methylation of Pivalophenone N−H Imines",

abstract = "Iron-catalyzed ortho C−H arylation and methylation reactions of pivalophenone N−H imines are reported. The pivaloyl N−H imine proved an excellent directing group for the arylation with diarylzinc reagents in the presence of an iron-diphosphine catalyst and 2,3-dichlorobutane at room temperature. A similar catalytic system also allowed methylation with Me3Al at 70 °C. The pivaloyl imine of the product could be readily converted to a cyano group, thus allowing convenient preparation of ortho-functionalized benzonitriles.",

keywords = "arylation, C−H activation, iron, methylation, organometallic reagents",

author = "Wengang Xu and Naohiko Yoshikai",

note = "Funding Information: This work was supported by the Ministry of Education (Singapore) and Nanyang Technological University (MOE2016-T2-2-043). Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

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doi = "10.1002/cssc.201900164",

language = "English",

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AU - Xu, Wengang

AU - Yoshikai, Naohiko

N1 - Funding Information: This work was supported by the Ministry of Education (Singapore) and Nanyang Technological University (MOE2016-T2-2-043). Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/7/5

Y1 - 2019/7/5

N2 - Iron-catalyzed ortho C−H arylation and methylation reactions of pivalophenone N−H imines are reported. The pivaloyl N−H imine proved an excellent directing group for the arylation with diarylzinc reagents in the presence of an iron-diphosphine catalyst and 2,3-dichlorobutane at room temperature. A similar catalytic system also allowed methylation with Me3Al at 70 °C. The pivaloyl imine of the product could be readily converted to a cyano group, thus allowing convenient preparation of ortho-functionalized benzonitriles.

AB - Iron-catalyzed ortho C−H arylation and methylation reactions of pivalophenone N−H imines are reported. The pivaloyl N−H imine proved an excellent directing group for the arylation with diarylzinc reagents in the presence of an iron-diphosphine catalyst and 2,3-dichlorobutane at room temperature. A similar catalytic system also allowed methylation with Me3Al at 70 °C. The pivaloyl imine of the product could be readily converted to a cyano group, thus allowing convenient preparation of ortho-functionalized benzonitriles.

KW - arylation

KW - C−H activation

KW - iron

KW - methylation

KW - organometallic reagents

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Iron-Catalyzed ortho C−H Arylation and Methylation of Pivalophenone N−H Imines

Abstract

Keywords

ASJC Scopus subject areas

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