Pd/Mn Bimetallic Relay Catalysis for Aerobic Aldoxime Dehydration to Nitriles

Abstract A Pd/Mn bimetal system was found to be an effective catalyst for dehydration of aldoximes to the useful nitriles under mild aerobic conditions. Different to the known metal‐catalyzed aldoxime dehydration reactions, this reaction very possibly proceeded via an alternative mechanism of Pd/Mn bimetal relay catalysis involving a Mn‐catalyzed aerobic oxidation of aldoximes to nitrile oxides by air and a Pd‐catalyzed oxygen transfer from the nitrile oxides to the solvent acetonitrile. This method tolerates a variety of substrates including sterically bulky ones and also the natural product derivative. magnified image