Cobalt-Catalyzed Chelation-Assisted Alkylation of Arenes with Primary and Secondary Alkyl Halides

Ke Gao; Takeshi Yamakawa; Naohiko Yoshikai

doi:10.1055/s-0033-1338658

Synthesis, Table of Contents

Synthesis 2014; 46(15): 2024-2039
DOI: 10.1055/s-0033-1338658

feature article

Cobalt-Catalyzed Chelation-Assisted Alkylation of Arenes with Primary and Secondary Alkyl Halides

Ke Gao

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore Fax: +65(6791)1961 Email: nyoshikai@ntu.edu.sg

,

Takeshi Yamakawa

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore Fax: +65(6791)1961 Email: nyoshikai@ntu.edu.sg

,

Naohiko Yoshikai*

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore Fax: +65(6791)1961 Email: nyoshikai@ntu.edu.sg

› Author Affiliations

Abstract

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Abstract

Cobalt–N-heterocyclic carbene catalytic systems have been developed for chelation-assisted ortho-alkylation of aromatic compounds with alkyl halides. Aryl imines can be selectively monoalkylated at room temperature by various primary or secondary alkyl chlorides or bromides. The catalytic system can also be applied to 2-arylpyridine derivatives, which in the absence of steric hindrance are amenable to dialkylation by an excess of the alkyl halide. Mechanistic experiments, including reactions of stereochemical probes and radical clocks, indicate that the reaction involves single-electron transfer from the cobalt center to the alkyl halide to form the corresponding alkyl radical, which has a finite lifetime before it undergoes C–C bond formation.

Key words

functionalization - catalysis - cobalt - alkylations - alkyl halides - radical reaction

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