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5-Hydroxymethyl-2-furfurylamine (5-HMFA) as an important 5-HMF derivative has been widely utilized in the manufacture of diuretics, antihypertensive drugs, preservatives and curing agents. In this work, an efficient chemoenzymatic route was constructed for producing 5-(hydroxymethyl)furfurylamine (5-HMFA) from biobased D -fructose in deep eutectic solvent Betaine:Glycerol-water. The introduction of Betaine:Glycerol could greatly promote the dehydration of D -fructose to 5-HMF and inhibit the secondary decomposition reactions of 5-HMF, compared with a single aqueous phase. D -Fructose (200 mM) could be catalyzed to 5-HMF (183.4 mM) at 91.7% yield by SG(SiO 2 ) (3 wt%) after 90 min in Betaine:Glycerol (20 wt%), and at 150 °C. E. coli AT exhibited excellent bio-transamination activity to aminate 5-HMF into 5-HMFA at 35 °C and pH 7.5. After 24 h, D -fructose-derived 5-HMF (165.4 mM) was converted to 5-HMFA (155.7 mM) in 94.1% yield with D -Ala ( D -Ala-to-5-HMF molar ratio 15:1) in Betaine:Glycerol (20 wt%) without removal of SG(SiO 2 ), achieving a productivity of 0.61 g 5-HMFA/(g substrate D -fructose). Chemoenzymatic valorization of D -fructose with SG(SiO 2 ) and E. coli AT was established for sustainable production of 5-HMFA, which has potential application.

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Significant Enhancement of 5-Hydroxymethylfural Productivity from D-Fructose with SG(SiO2) in Betaine:Glycerol–Water for Efficient Synthesis of Biobased 5-(Hydroxymethyl)furfurylamine