Iron-catalyzed C-C bond formation at alpha-position of aliphatic amines via C-H bond activation through 1,5-hydrogen transfer

Naohiko Yoshikai; Adam Mieczkowski; Arimasa Matsumoto; Laurean Ilies; Eiichi Nakamura

doi:10.1021/ja100651t

Iron-catalyzed C-C bond formation at alpha-position of aliphatic amines via C-H bond activation through 1,5-hydrogen transfer

J Am Chem Soc. 2010 Apr 28;132(16):5568-9. doi: 10.1021/ja100651t.

Authors

Naohiko Yoshikai¹, Adam Mieczkowski, Arimasa Matsumoto, Laurean Ilies, Eiichi Nakamura

Affiliation

¹ Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033.

PMID: 20361736
DOI: 10.1021/ja100651t

Abstract

C-C bond formation reactions that take place through organoiron species sometimes exhibit radical-like character. The reaction of N-(2-iodophenylmethyl)dialkylamine with a Grignard or diorganozinc reagent in the presence of a catalytic amount of Fe(acac)(3) gives the product resulting from arylation, alkenylation, or alkylation of the sp(3) C-H bond next to the amine group in good to excellent yield. Mechanistic studies including labeling experiments indicate that the reaction involves radical translocation triggered by the formation of a radical-like species by removal of the iodide group.