LAUSR

A molybdenum N‐heterocyclic carbene catalyst has been developed for the synthesis of imines from primary alcohols and amines with the liberation of dihydrogen. The catalyst is generated in situ from molybdenum hexacarbonyl, 1,3‐dicyclohexylimidazolium chloride and potassium tert‐butoxide and is further stabilized by the phosphine ligand dppe. Imines are formed in moderate to good isolated yields and a variety of alcohols and amines can be employed in the reaction including anilines. The transformation constitutes the first example of a homogeneous molybdenum‐catalyzed acceptorless dehydrogenative coupling with alcohols and is believed to proceed by formation of a cis‐coordinated molybdenum bis‐N‐heterocyclic carbene complex, which performs an oxidative addition to the alcohol, β‐hydride elimination and reductive elimination of dihydrogen.