Biocatalytic Transformation of 5-Hydroxymethylfurfural into High-Value Derivatives: Recent Advances and Future Aspects

Abstract

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.

Sustainable Aromatic Aliphatic Polyesters and Polyurethanes Prepared from Vanillin-Derived Diols via Green Catalysis

“…With the vanillin-based diol monomer in hand, we prepared polyesters and polyurethanes with diacyl chlorides and diisocyanatos, respectively according to the literature methods [20,39]. A series of polyesters were obtained via direct acylation between HMEO and acyl chlorides including oxalyl chloride (OC), succinyl chloride (SC) [40], terephthaloyl chloride (TC) [41] and 2,5-furandicarbonyl dichloride (FC) [42,43]. The 2,5-furandicarboxylic acid has been extensively studied in bio-based polymers [44][45][46].…”

Enzymatic synthesis of biobased aliphatic–aromatic oligoesters using 5,5′-bis(hydroxymethyl)furoin as a building block

“…We hypothesized that, by analogy with the above mentioned enzymatic synthesis of BHMF-based polyesters, 21 the desired DHMF-based linear polyesters could be obtained by exploiting lipases selectivity although, until now, the enzymatic esterication of DHMF has never yet described. 29 Herein we reported the unprecedented enzymatic esterication of DHMF. Furthermore, thanks to the selectivity shown by Candida anctartica lipase B (CALB) for the primary alcoholic groups of DHMF, the reaction conducted under appropriate conditions, has been exploited to synthetize fully bio-based aromatic-aliphatic linear oligoesters, bearing free secondary hydroxyl groups on the polymer backbone.…”

Selective Biosynthesis of Furoic Acid From Furfural by Pseudomonas Putida and Identification of Molybdate Transporter Involvement in Furfural Oxidation

“…HMF to 5-hydroxymethylfuroic acid (HMFCA), 2,5diformylfuran, 5-formylfuroic acid, and 2,5-furandicarboxylic acid (FDCA) (Qin et al, 2015;Hu et al, 2018). Up to now, chemocatalytic approaches for selective oxidation of FAL and HMF have been extensively studied, which often involve the use of toxic and hazardous reagents and solvents, the harsh conditions, as well as the low selectivity (Mariscal et al, 2016;Sajid et al, 2018).…”