Aerobic oxidative coupling of alcohols and amines over Au–Pd/resin in water: Au/Pd molar ratios switch the reaction pathways to amides or imines

Abstract

A facile switch of the reaction pathways of aerobic oxidative coupling of alcohols and amines from amidation to imination was realized for the first time by tuning the Au/Pd ratios in ion-exchange resin supported Au–Pd alloy catalysts (Au–Pd/resin). Amides were obtained with high yields on Au₆Pd/resin while imines were obtained over AuPd₄/resin. Various alcohols and amines underwent oxidative coupling smoothly in water to afford the desired products with good to excellent yields. Further investigation on the reaction mechanism suggested the synergistic effect between Au and Pd determined the adsorption strength of the aldehyde intermediate, which in turn dictated the reaction pathways. That is, on Au-rich alloys (e.g., Au₆Pd) absorbed aldehyde species was formed, followed by further oxidation to yield amides, while on Pd-rich alloys (e.g., AuPd₄), free aldehyde was generated, which then underwent condensation with amines to produce imines. The discovery might provide avenues to develop new efficient catalysts for the green synthesis of special chemicals.