Role of Anions in 5‐Hydroxymethylfurfural Solvation in Ionic Liquids from Molecular Dynamics Simulations

The proper selection of solvents for biomass upgrading is a crucial task as it should carefully balance the enhancement of reactivity with a facile product recovery. A challenging case is the conversion of glucose and fructose to 5-hydroxymethylfurfural (HMF). Ionic liquids (ILs) are often employed to boost the activity and selectivity of this process, although the isolation of HMF from the medium remains a major drawback. To investigate such solvent effects in a realistic (dynamic) environment, classical molecular dynamics (MD) simulations of HMF are performed in imidazolium-based ILs with different anions. Several parameters are identified that directly control HMF-anion interactions, which may hamper product separation, as well as HMF-HMF contacts, which can promote undesired side-reactions. These computational results would guide future high-throughput screenings of new and improved IL media.