Rhenium-Catalyzed Deoxydehydration of Diols and Polyols

The substitution of platform chemicals of fossil origin by biomass‐derived analogues requires the development of chemical transformations capable of reducing the very high oxygen content of biomass. One such reaction, which has received increasing attention within the past five years, is the rhenium‐catalyzed deoxydehydration (DODH) of a vicinal diol into an alkene; this is a model system for abundant polyols like glycerol and sugar alcohols. The present contribution includes a review of early investigations of stoichiometric reactions involving rhenium, diols, and alkenes followed by a discussion of the various catalytic systems that have been developed with emphasis on the nature of the reductant, the substrate scope, and mechanistic investigations. Taking a shortcut! Recent developments in the rhenium‐catalyzed deoxydehydration reaction are reviewed. Although the reaction is formally a deoxygenation and a dehydration, the use of transition metal catalysis opens up new possibilities. The focus is on recent developments of the substrate scope, alternative reductants, and mechanistic investigations.