Accelerating Selective Oxidation of Biomass-Based Hydroxyl Compounds with Hydrogen Bond Acceptors.

Hydrogen-bonding-initiated self-association makes the valorization of biomass-based hydroxyl compounds a formidable challenge at high concentration. Apart from enhancing the dehydration reaction of hydroxyl compounds with the noncovalent medium effects, insights into how these effects can be exploited to optimize the oxidative reactivity of concentrated hydroxyl compounds remain unclear. Herein, we elucidate that deaggregation of hydroxyl groups with a catalytic number of hydrogen bond acceptors is essential in improving the reactivity of the aerobic oxidation of biomass-based neat aromatic alcohols over the vanadium-based catalyst. The neat 5-hydroxymethylfurfural (HMF) deaggregated with 25 mol % N,N-dimethylformamide (DMF) shows a >7-fold increase in reactivity to produce corresponding aldehydes with excellent selectivity, in stark contrast to the contrary deactivation of reaction in excessive DMF.