Direct Deoxydehydration of Cyclic trans-Diol Substrates: An Experimental and Computational Study of the Reaction Mechanism of Vanadium(V)-based Catalysis*.

The deoxydehydration of carbohydrates represents a key target to leverage renewable biomass resources chemically. Using a vanadium(V)-based catalyst, it was possible to directly deoxydehydrate cyclic trans-diol substrates. Accompanying mechanistic characterisation of this process by density functional calculations pointed to an energetically tractable route for deoxydehydration of cyclic trans-diol substrates involving stepwise cleavage of the diol C-O bonds via the triplet state; experimentally, this was supported by light dependence of the reaction. Calculations also indicated that cyclic cis-diols and a linear diol substrate could additionally proceed by a concerted singlet DODH mechanism. This work potentially opens a new and cost-effective way to efficiently convert carbohydrates of trans-diol stereochemistry into alkenes.