Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion

We describe the use of simple copper‐salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations. Not satisfied with an observer role, the counteranion determined the outcome of the copper‐catalyzed aerobic oxidation of amines to nitriles or imines (see scheme). Selectivity was controlled by ion pairing to the counterion in these reactions, which proceeded at ambient temperature and pressure without expensive ligands or additives.