Iridium-Catalyzed Enantioselective Allenylic Cyanomethylation

The poor acidity of acetonitrile restricted its utility as a C2 synthon of a cyanomethyl group for incorporation into organic compounds. We now employed a 2-azido allylic alcohol as an acetonitrile enolate surrogate for the first enantioselective allenylic cyanomethylation. This mild and base-free protocol utilizes cooperative iridium and Lewis acid catalysis for the activation of branched allenylic alcohols to deliver α-allenylic acetonitriles in moderate to good yields with excellent enantioselectivity.