Base-catalyzed switchable reactivity of N-acyl-α-aminonitriles: oxidative decyanation to imides and hydrolysis to amides in batch and flow conditions

Abstract

A base-catalyzed, transition-metal-free synthesis of imides and amides from N-acyl-α-aminonitriles is reported under batch and continuous-flow conditions. Imides are selectively formed in the presence of open air or an O₂ atmosphere, while degassed H₂O–DMSO conditions afford amides. The protocol shows good scalability and broad functional-group tolerance, and enables late-stage modification of pharmaceutically relevant, ibuprofen-derived substrates; mechanistic studies suggest oxidative decyanation and nitrile hydrolysis pathways for imides and amides, respectively.