Molybdenum-Catalyzed Deoxydehydration of Vicinal Diols

The commercially available (NH4)6Mo7O24 and other molybdenum compounds are shown to be viable substitutes for the typically employed rhenium compounds in the catalytic deoxydehydration of aliphatic diols into the corresponding alkenes. The transformation, which represents a model system for the various hydroxyl groups found in biomass‐derived carbohydrates, can be conducted in an inert solvent (dodecane), under solvent‐free conditions, and in a solvent capable of dissolving biomass‐derived polyols (1,5‐pentanediol). The reaction is driven by the simultaneous oxidative deformylation of the diol resulting in an overall disproportionation of the substrate. Disproportionating Biomass!: The commercially available (NH4)6Mo7O24 and other molybdenum compounds are shown to catalyze the deoxydehydration of biomass‐derived diols to alkenes. In the reaction, one half of the diol is consumed as a sacrificial reductant, which undergoes oxidative deformylation, that is, a formal disproportionation.