Metalated nitriles: halogen-metal exchange with alpha-halonitriles

Org Lett. 2004 Feb 19;6(4):501-3. doi: 10.1021/ol036202s.

Abstract

[reaction: see text] Alpha-halonitriles react with organometallic reagents in a facile halogen-metal exchange. The halogen-metal exchange is extremely fast with Grignard and alkyllithium reagents, generating metalated nitriles in situ with aldehyde, ketone, acid chloride, and acyl cyanide electrophiles. Sequential halogen-metal exchange and methylation of conformationally constrained nitriles is highly stereoselective and consistent with a retentive alkylation of a C-magnesiated nitrile.