Selective Hydrogenation of Nitriles to Primary Amines Catalyzed by a Polysilane/SiO2‐Supported Palladium Catalyst under Continuous‐Flow Conditions

Abstract Hydrogenation of nitriles to primary amines with heterogeneous catalysts under liquid‐phase continuous‐flow conditions is described. Newly developed polysilane/SiO 2 ‐supported Pd was found to be an effective catalyst and various nitriles were converted into primary amine salts in almost quantitative yields under mild reaction conditions. Interestingly, a complex mixture was obtained under batch conditions. Lifetime experiments showed that this catalyst remained active for more than 300 h ( TON ≥10 000) without loss of selectivity and no metal leaching from the catalyst occurred. By using this continuous‐flow hydrogenation, synthesis of venlafaxine, an antidepressant drug, has been accomplished.