Synthesis 2014; 46(15): 2024-2039
DOI: 10.1055/s-0033-1338658
feature article
© Georg Thieme Verlag Stuttgart · New York

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: [email protected]
,
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: [email protected]
,
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: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 07 April 2014

Accepted after revision: 12 June 2014

Publication Date:
09 July 2014 (online)


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.

Supporting Information

 
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