Chemoenzymatic Synthesis of 5‐Hydroxymethylfurfural (HMF)‐Derived Plasticizers by Coupling HMF Reduction with Enzymatic Esterification

Abstract

Biobased plasticizers, as substitutes for phthalates, have been synthesized from 5‐hydroxymethylfurfural (HMF) and carboxylic acids (or esters) through a chemoenzymatic cascade process that involves as its first step the reduction of 5‐hydroxymethylfurfural into 2,5‐bis(hydroxymethyl)furan (BHMF), followed by the esterification of BHMF with carboxylic acids (or esters) by using a supported lipase (Novozym 435). The reduction of HMF into BHMF is performed by using monodisperse metallic Co nanoparticles with a thin carbon shell (Co@C) with high activity and selectivity. After optimization of reaction conditions (temperature, hydrogen pressure, and solvent), it is possible to achieve 97 % conversion of HMF with 99 % selectivity to BHMF after 2 h reaction time. The reduction of HMF and esterification of BHMF using carboxylic acids or vinyl esters as acyl donors by lipase are optimized separately in batch and in fixed‐bed continuous reactors. The coupling of two flow reactors (for reduction and subsequent esterification) working under optimized reaction conditions affords the diesters of BHMF in roughly 90 % yield with no loss of activity during 60 h of operation.

Recent Advances in the Catalytic Hydroconversion of 5-Hydroxymethylfurfural to Valuable Diols

“…As a result, Co, which is a transition metal, has been widely used for the catalytic conversion of HMF to BHMF. A hydrothermally synthesized monodispersed metallic Co catalyst, Co@C, was used in the selective hydrogenation of HMF, resulting in a 96.0% yield of BHMF at 110 °C and 1 MPa H 2 for 6 h with methanol as the solvent (Arias et al, 2020). According to this study, the excellent performance of the Co@C catalyst is attributable to the minuscule Co 0 nanoparticles coated on the surface of the carbon shell, which provide sufficient catalytic activity.…”

Thieme‐IUPAC‐Preis:A. Li / Springer‐Preis für Heterocyclenchemie: C. D. Vanderwal / IACS‐Preise:X. Hu, A. Corma

“…Über Corma, Mitglied des Internationalen Beirats der Angewandten Chemie und Ehrenmitglied des Beirats von ChemCatChem , wurde hier zuletzt 2018 als Gewinner der Blaise‐Pascal‐Medaille in Chemie berichtet . Seine Gruppe stellte in ChemSusChem die Synthese von 5‐Hydroxymethylfurfural abgeleiteter Weichmacher und die Umwandlung von Lävulinsäuremethylester in biobasierte Tenside und Schmiermittel vor …”

Thieme–IUPAC Prize:A. Li / Springer Heterocyclic Chemistry Award:C. D. Vanderwal / IACS Awards:X. Hu, A. Corma

“…Corma, a member of the International Advisory Board of Angewandte Chemie and of the Honorary Board of ChemCatChem , was last featured in this section when he was awarded the Blaise Pascal Medal in Chemistry in 2018 . In two Full Papers in ChemSusChem his group recently reported on the synthesis of 5‐hydroxymethylfurfural‐derived plasticizers and on transforming methyl levulinate into biosurfactants and biolubricants …”