Copper-Catalyzed Claisen Rearrangement with AIBN and Allylic Alcohols.

A novel and succinct method for the synthesis of N -cyanomethyl amides from allylic alcohols with AIBN as the nitrile source is developed. Owing to the coordination effect with the copper catalyst, a ketenimine intermediate is formed via couplings of isobutyronitrile radicals. The copper-activated ketenimine could subsequently be intercepted by allylic alcohols and undergo Claisen rearrangement to furnish N -cyanomethyl amides. Further functional group transformations of the N -cyanomethyl amide products are also described.