Ultrathin Platinum Nanowire Catalysts for Direct CN Coupling of Carbonyls with Aromatic Nitro Compounds under 1 Bar of Hydrogen

Traditionally important in the pharmaceutical, agrochemical, and synthetic dye industries, CN coupling has proved useful for the preparation of a number of valuable organic compounds. Here, a new method for the direct one‐pot reductive CN coupling from carbonyl and aromatic nitro compounds is described. Employing ultrathin platinum nanowires as the catalyst and hydrogen as the reducing agent, N ‐alkylamines were achieved in high yields. Debenzylation products were not detected after prolonged reaction times. Time‐dependent analysis, ReactIR spectroscopy and DFT calculations revealed that the CN coupling proceeded through a different mechanism than traditional “reductive amination.” N ‐Alkylamines were directly obtained by intermolecular dehydration over platinum nanowires under a hydrogen atmosphere, instead of intramolecular water elimination and imine hydrogenation.