Iron-catalyzed C-H bond activation for the ortho-arylation of aryl pyridines and imines with Grignard reagents

Naohiko Yoshikai, Sobi Asako, Takeshi Yamakawa, Laurean Ilies, Eiichi Nakamura

Research output: Contribution to journalArticle

69 Citations (Scopus)

Abstract

Direct arylation of the ortho-C-H bond of an aryl pyridine or an aryl imine with an aryl Grignard reagent has been achieved by using an iron-diamine catalyst and a dichloroalkane as an oxidant in a short reaction time (e.g., 5 min) under mild conditions (0 °C). The use of an aromatic co-solvent, such as chlorobenzene and benzene, and slow addition of the Grignard reagent are essential for the high efficiency of the reaction. The present arylation reaction has distinct merits over the previously developed reaction that used an arylzinc reagent, such as its reaction rate and atom economy. Selective C-H bond activation occurs in the presence of a leaving group, such as a tosyloxy, chloro, and bromo group. Studies on a stoichiometric reaction and kinetic isotope effects shed light on the reaction intermediate and the C-H bond-activation step.

Original languageEnglish
Pages (from-to)3059-3065
Number of pages7
JournalChemistry - An Asian Journal
Volume6
Issue number11
DOIs
Publication statusPublished - Nov 4 2011

Keywords

  • C-H activation
  • Grignard reagent
  • biaryls
  • cross-coupling
  • iron

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry

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