Room-Temperature Decarboxylative Amination of Electron-Deficient (Hetero)Aromatic Carboxylic Acids

Decarboxylative amination reactions offer the opportunity to access (hetero)aromatic amines from readily available carboxylic acid starting materials. However, the reliance of the Curtius rearrangement on organoazides introduces safety concerns, while more recent transition-metal-mediated approaches suffer from high reaction temperatures and limited substrate scopes. Here, we demonstrate a room-temperature decarboxylative amination to generate a wide array of primary (hetero)aromatic amines mediated by N-fluorobenzenesulfonimide (NFSI). The broad functional group tolerance of this reaction enables efficient amination of biologically relevant small molecules. Mechanistic studies suggest that NFSI provides access to an activated sulfonimide intermediate, a functional equivalent to acyl azide intermediates, while avoiding the hazards associated with organoazides.