Oxidative Coupling of Alcohols and Amines over Bimetallic Unsupported Nanoporous Gold: Tailored Activity through Mechanistic Predictability

An unsupported nanoporous gold catalyst is employed for the direct coupling of primary alcohols and amines to the corresponding amides in the liquid phase. Among others, the reaction of methanol and dimethylamine to the industrially relevant dimethylformamide proceeds smoothly at 40 degrees C (turnover frequency approximate to 40 h(-1)). The activation of molecular oxygen is identified as a key parameter. Doping of the unsupported catalyst by an admetal (Ru, Ag) is used to increase the activity of the catalyst considerably for this reaction (turnover frequency approximate to 100 h(-1)).