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In recent years, 2,5-dihydroxymethylfuran (DHMF), which can be produced by the selective hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF), has attracted great attention and interest of many scientists because of its peculiar symmetrical structure and wide potential applications. At present, studies of the production of DHMF are quickly progressing, with productive approaches being increasingly developed, and many crucial achievements have been continually obtained. However, to date, a special and real-time review of this research area is still lacking. To gain more insight into the current research situation, this review comprehensively summarizes and discusses state-of-the-art advancements of the production of DHMF from HMF via various chemocatalytic pathways, such as conventional hydrogenation, transfer hydrogenation, electrocatalytic hydrogenation, photocatalytic hydrogenation, disproportionation reaction, and biocatalytic pathways. Meanwhile, this review also systematically outlines the latest results on the further transformation of DHMF into value-added derivatives via etherification, polymerization, and rearrangement.

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Catalytic transformation of biomass-derived 5-hydroxymethylfurfural (HMF) into a series of high-value derivatives, such as 2,5-diformylfuran, 5-hydroxymethyl-2-furancarboxylic acid, 5-formyl-2-furancarboxylic acid, 2,5-furandicarboxylic acid, 2,5-dihydroxymethylfuran, 5-alkanoyloxymethylfurfural, 5,5-bis­(hydroxymethyl)­furoin and 5-hydroxymethylfurfurylamine, is a very important research field in the biorefinery process. For a long time, chemocatalytic pathways have been the main transformation methods of HMF, and so, they have been widely studied in recent years. However, considering some unavoidable issues of chemocatalytic pathways, biocatalytic pathways with many advantages, such as higher selectivity, gentler condition, lower investment and environmental friendliness, should be a promising alternative, and unfortunately, they have not yet attracted enough attention until now. To better understand the current research status, this review primarily retrospects and describes the discovery and development of biocatalytic transformation of HMF, and then systematically summarizes and discusses the latest studies and advancements on the biocatalytic transformation of HMF through oxidation, reduction, esterification, carboligation and amination in the presence of the corresponding enzymes or whole-cells. Furthermore, this review also proposes a few possible research trends in the future studies, aiming at providing a few helpful and feasible references and supports for the biocatalytic transformation of HMF in much more economical and effective ways.

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