An Umpolung Route to Amides from α-Aminonitriles under Metal-Free Conditions

A metal-free, base-mediated decyanation of alpha-aminonitriles has been developed to synthesize secondary and tertiary amides using O-2 or air as an amide oxygen source. Radical scavenging studies disclosed that the cleavage of C-CN bond may proceed via an anionic pathway. The practicality of the work was also demonstrated through an in situ generated alpha-aminonitriles from corresponding aldehydes and amines to afford amides. The important features of this work include broad functional group compatibility, 41% to 89% product yields, gram-scale synthesis of 2 degrees and 3 degrees amides, broad substrate scope, and an umpolung strategy.