A Hybrid Process for Valorization of D-Fructose to 2,5-Bis(hydroxymethyl)furan by Bridging Chemocatalysis and Biocatalysis in a Betaine:Benzenesulfonic Acid System

Biobased 2,5-bis(hydroxymethyl)furan is a versatile building block for the production of drugs, polymers, crown ethers, bioactive compounds, and value-added intermediates. To explore a more efficient route to synthesize 2,5-bis(hydroxymethyl)furan, a tandem transformation by quick dehydration with a deep eutectic solvent betaine:benzenesulfonic acid (Bet:BSA) and mild bioreduction with recombinant Escherichia coli (E. coli) DCF was developed for converting D-fructose into 2,5-bis(hydroxymethyl)furan. The 5-hydroxymethylfuran yield reached 62.3 +/- 1.6% (based on D-fructose) in Bet:BSA at 120 ? after a short time (2 min). D-Fructose-valorized 5-hydroxymethylfuran was biologically transformed to 2,5-bis(hydroxymethyl)furan by newly constructed recombinant E. coli DCF containing reductase and formate dehydrogenase at 40 & DEG;C and pH 7.5 after 48 h, with a yield of 99.6 & PLUSMN; 0.1% (based on 5-hydroxymethylfuran) in Bet:BSA-water containing the cosubstrate HCOONa (5-HMF-to-HCOONa molar ratio, 1:2.5). Meanwhile, 150 mM commercial 5-hydroxymethylfuran was transformed into 2,5-bis(hydroxymethyl)furan in a yield of 94.4 & PLUSMN; 0.9%. An efficient hybrid process was constructed to valorize D-fructose to 2,5-bis(hydroxymethyl)furan in Bet:BSAwater, which has good industrial application potential.