Selective cleavage of the C-C bonds of aminoethyl groups, via a multistep pathway, by a pincer iridium complex

Xiawei Zhang; Thomas J Emge; Rajshekhar Ghosh; Alan S Goldman

doi:10.1021/ja051300p

Selective cleavage of the C-C bonds of aminoethyl groups, via a multistep pathway, by a pincer iridium complex

J Am Chem Soc. 2005 Jun 15;127(23):8250-1. doi: 10.1021/ja051300p.

Authors

Xiawei Zhang¹, Thomas J Emge, Rajshekhar Ghosh, Alan S Goldman

Affiliation

¹ Department of Chemistry, Rutgers, The State University of New Jersey, Piscataway, NJ 08854, USA.

PMID: 15941235
DOI: 10.1021/ja051300p

Abstract

A pincer-ligated iridium complex is found to react with N-ethylamines, HN(Et)R (R = cyclohexyl, tert-butyl, ethyl), to give the corresponding iridium isocyanide complexes (PCP)Ir(CH3)(H)(CNR) (PCP = kappa3-2,6-(tBu2PCH2)2C6H3). This novel, regioselective C-C bond cleavage reaction occurs readily under mild conditions (25-45 degrees C). The reaction is shown to proceed via initial dehydrogenation of the amine to give the corresponding imine (N-ethylidenealkylamine). The ethylidene sp2 C-H bond then undergoes addition to iridium, followed by methyl migration.