Recent Advances in the Development of 5‐Hydroxymethylfurfural Oxidation with Base (Nonprecious)‐Metal‐Containing Catalysts

Abstract

5‐Hydroxymethylfurfural (HMF) is one of the versatile platform molecules that can be derived from biomass, and a promising starting substrate for producing 2,5‐diformylfuran (DFF) and 2,5‐furandicarboxylic acid (FDCA). DFF is a platform chemical with applications in pharmaceuticals, macrocyclic ligands, and functional polymeric materials. Importantly, FDCA is being considered as a potential alternative to replace terephthalic acid for producing the bioplastic polyethylene furanoate, instead of polyethylene terephthalate, by blending with ethylene glycol. A significant number of studies have focused on the oxidation of HMF to FDCA with metal‐containing heterogeneous catalysts in both aqueous and organic media in the presence of peroxides/air/molecular oxygen as the oxidant. In this regard, articles have recently been published related to HMF oxidation with base (nonprecious)‐metal‐containing catalysts that exhibit appealing activity towards DFF or FDCA in terms of yield. Thus, this Minireview focuses on recent developments in efficient transformations of HMF to DFF and FDCA with base‐metal‐containing heterogeneous catalysts in aqueous and organic media. This review further focuses on the direct transformation of glucose/fructose to DFF and/or FDCA with nonprecious‐metal‐containing catalysts in various solvents. Photocatalytic approaches for HMF oxidation with nonprecious metal‐ containing catalysts are also briefly discussed.

Continuous‐Flow Oxidation of HMF to FDCA by Resin‐Supported Platinum Catalysts in Neat Water

“…Adoption of water as a solvent is, therefore, an attractive option. In this case, current limitations are related to: use of batch setups and expensive gold catalysts, poor FDCA solubility, need of excess of metal catalyst or strong base additives (e.g., NaOH, K 2 CO 3 ), harsh reaction conditions, corrosion, and catalyst deactivation . The development of cleaner and more environmentally acceptable methods for FDCA production is therefore of utmost importance …”

“…[8,9] Adoption of water as as olvent is, therefore, an attractive option.I nt his case, current limitations are relatedt o: use of batch setups and expensiveg old catalysts, poor FDCA solubility,n eed of excesso fm etal catalyst or strongb ase additives (e.g.,N aOH, K 2 CO 3 ), harsh reaction conditions, corrosion, andc atalyst deactivation. [10,11] The development of cleaner and more environmentally acceptable methods for FDCA production is therefore of utmost importance. [12,13] Herein, we report the synthesis and characterization of a heterogeneous, resin-supported Pt catalysta nd its use in the one-pot oxidation of HMF to FDCA in neat water under continuous-flow conditions.…”

Functionalized expanded corn starch‐anchored Cu(I): An efficient and recyclable catalyst for oxidation of 5‐hydroxymethylfurfural to 2,5‐diformylfuran

“…DFF was purified by flash column chromatography on silica gel (eluent was petroleum ether-EtOAc, 7:3), where a colorless band was collected and the solvent removed in vacuo resulting in a white crystalline compound. 1…”

“…2,5‐Diformylfuran (DFF) is a versatile compound that has various applications, including as a polymeric monomer and a promising cross‐linking agent for battery separation, in pharmaceuticals, antifungal agents, furan–urea resins, heterocyclic ligands and other value added products, which is synthesized predominantly via the oxidation of 5‐hydroxymethylfurfural (HMF). However, this transformation can be accompanied by the formation of several other kinds of furan compounds like 2,5‐furandicarboxylic acid, 5‐formyl‐2‐furancarboxylic acid and 5‐hydroxymethyl‐2‐furancarboxylic acid .…”

Continuous Flow Synthesis of Bimetallic AuPd Catalysts for the Selective Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid

“…A more environmentally friendly way to produce FDCA is by the selective oxidation of HMF with molecular oxygen; this reaction is typically carried out in water as solvent and it is catalysed by heterogeneous catalysts, particularly by supported noble metal nanoparticles. [18][19][20][21][22] Ru-, Pt-and Pd-based catalysts have all shown high performance in both activity and selectivity towards the desired product, although these catalysts have often shown poor stability against deactivation, particularly with respect to oxygen poisoning and metal leaching. [23][24][25][26][27] Aubased catalysts have recently attracted attention in the aerobic oxidation of organic compounds due to their superior stability to water and oxygen compared with conventional liquid-phase oxidation catalysts.…”