Aerobic Oxidation of 5‐Hydroxymethylfurfural via Hydrogen Bonds Reconstruction with Ternary Deep Eutectic Solvents.

Hydrogen bonding effect exists widely in various chemical and biochemical systems, primarily stabilizing the molecular structure as a positive factor. However, the presence of intermolecular hydrogen bonds among biomass molecules results in a formidable challenge for the efficient utilization of biomass resources. Here in, a novel strategy of "hydrogen bonds reconstruction" was developed by a series of ternary deep eutectic solvent (DESs) as molecular scissors, which disrupting the initial intermolecular hydrogen bonds and reconstructing the new ones to increase the reactivity of the biomass‐based compound. The DESs played a crucial role in enhancing the reactivity of 5‐hydroxymethylfurfural (HMF) and promoting its oxidation through reconstructing the hydrogen bonds interactions. Furthermore, DESs was also found to activate the Anderson‐type catalyst Na5IMo6O24 (IMo6) through an electron‐transfer mechanism, which facilitated the generation of oxygen vacancies and significantly enhances its ability to activate molecular oxygen. With this novel catalytic system, oxidation of HMF exhibited remarkable efficiency as HMF was almost entirely converted into FFCA with an impressive yield of 98 % under the optimized conditions. This finding offers novel insights into the utilization of biomass resources and endows the solvent with new functions in the chemical reaction. [ABSTRACT FROM AUTHOR]