Nickel-catalyzed ring-opening hydroacylation of methylenecyclopropanes: synthesis of gamma,delta-unsaturated ketones from aldehydes

Hiroki Taniguchi; Toshimichi Ohmura; Michinori Suginome

doi:10.1021/ja9046894

Nickel-catalyzed ring-opening hydroacylation of methylenecyclopropanes: synthesis of gamma,delta-unsaturated ketones from aldehydes

J Am Chem Soc. 2009 Aug 19;131(32):11298-9. doi: 10.1021/ja9046894.

Authors

Hiroki Taniguchi¹, Toshimichi Ohmura, Michinori Suginome

Affiliation

¹ Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan.

PMID: 19637868
DOI: 10.1021/ja9046894

Abstract

A nickel-catalyzed intermolecular hydroacylation of methylenecyclopropanes (MCPs) has been developed. The reaction proceeds with stereospecific cleavage of the proximal C-C bond of the cyclopropane ring to give gamma,delta-unsaturated ketones with high diastereoselectivities. A nickel catalyst generated in situ from Ni(cod)(2) and P(n-Bu)(3) with a P/Ni ratio of 1:1 is effective for the hydroacylation, in which benzaldehyde derivatives, heteroaryl aldehydes, and aliphatic aldehydes react with MCPs at 60-100 degrees C to afford the corresponding ketones in high yields.