Biocatalytic Valorization of Biobased 5-Hydroxymethylfurfural to 5-Hydroxymethyl-2-furfurylamine in a Three-Constituent Deep Eutectic Solvent–Water System

Abstract

5-Hydroxymethyl-2-furfurylamine (HMFA), as an important 5-hydroxymethylfurfural (5-HMF) derivative, has many potential applications in the preparation of diuretics, antihypertensive drugs, preservatives, and curing agents. In this work, highly efficient valorization of biomass-derived D-fructose into HMFA was attempted via a cascade reaction in a three-constituent deep eutectic solvent (3c-DES)−H 2 O. Using D-fructose (63.0 g/L) as a raw material, the yield of 5-HMF reached 68.2% in 3c-DES malic acid/glycerol/betaine−H 2 O (9:91, wt/wt) (pH 2.3) at 170 °C in 30 min. Whole cells of Escherichia coli CV harboring transaminase were utilized to valorize biomass-derived 5-HMF to HMFA at pH 8.0 and 30 °C using amine donor L-alanine. The valorization of 600 mM commercial 5-HMF gave a 93.2% yield of HMFA with 99.2% selectivity. In addition, CV cells transformed D-fructosevalorized 5-HMF into HMFA in 94.1% yield in 3c-DES malic acid/glycerol/betaine−H 2 O. This approach provided a sustainable and eco-efficient idea for chemoenzymatically valorizing biomass-derived D-fructose to HMFA.

Improved Synthesis of Furfurylamine from a High Titer of Biomass-Derived Furfural by a Thermostable Triple Mutant ω-Transaminase in a Three-Component Deep Eutectic Solvent ChCl/Lactic Acid/Malonic Acid System

“…29 It could be catalyzed to HMF by designed 3c-DES (betaine/glycerin/malic acid). 30 It could be seen that DES as a green catalyst had a good application in biomass recycling. In this work, DES ChCl/MA [preparation conditions: malonic acid (MA) and lactic acid (LA) were mixed in a molar ratio of 1:1 at 80 °C and 500 rpm for 20 min], ChCl/LA (preparation conditions: ChCl and LA were mixed in a molar ratio of 1:1 at 80 °C and 500 rpm for 20 min), and 3c-DES ChCl/MA/LA (preparation conditions: ChCl, MA, and LA were mixed in a molar ratio of 1:1:1 at 80 °C and 500 rpm for 20 min) could promote the formation of FAL compared to that in water (Figure 2a).…”

“…DES, which is composed of hydrogen-bond acceptors and hydrogen-bond donors, can catalyze the transformation of lignocellulose to biobased products and has been widely used in the field of green bioenergy. , d -Fructose was efficiently dehydrated to form HMF by DES betaine/lactic acid . It could be catalyzed to HMF by designed 3c-DES (betaine/glycerin/malic acid) . It could be seen that DES as a green catalyst had a good application in biomass recycling.…”

Combination of Enzymes and Deep Eutectic Solvents as Powerful Toolbox for Organic Synthesis

“…Remarkably, the one-pot procedure afforded enantiopure biaryl amines ( ee values as high as 99%) as the final products, without the need for extensive purification, as a simple solvent extraction was sufficient to separate the hydrophilic components (including those of the DES) from the product, which then just required a filtration over silica [ 112 ]. Some efforts to the application of transaminase biochemistry in DESs have been dedicated by the group of He to the conversion of furfural and 5-hydroxymethylfurfural ( Table 9 , entry 6) into the corresponding furfuryl amines, in the framework of the valorisation of lignocellulosic biomass, such as sugarcane bagasse [ 113 ], corncob [ 114 ], and sugar [ 115 ]. The biomass was first processed to obtain the furan derivatives, either through a tin-based heterogeneous catalyst, obtained exploiting waste shrimp shells, in ChCl/EG or ChCl/Gly DESs and H 2 O as cosolvent [ 113 , 114 ] or through dehydration in a malic acid (MA)Gly/betaine (Bet) DES with H 2 O as cosolvent, in the absence of any catalyst [ 115 ].…”

“…Some efforts to the application of transaminase biochemistry in DESs have been dedicated by the group of He to the conversion of furfural and 5-hydroxymethylfurfural ( Table 9 , entry 6) into the corresponding furfuryl amines, in the framework of the valorisation of lignocellulosic biomass, such as sugarcane bagasse [ 113 ], corncob [ 114 ], and sugar [ 115 ]. The biomass was first processed to obtain the furan derivatives, either through a tin-based heterogeneous catalyst, obtained exploiting waste shrimp shells, in ChCl/EG or ChCl/Gly DESs and H 2 O as cosolvent [ 113 , 114 ] or through dehydration in a malic acid (MA)Gly/betaine (Bet) DES with H 2 O as cosolvent, in the absence of any catalyst [ 115 ]. Then, in the same reaction medium, recombinant E. coli whole cells were employed to promote the transamination of the aldehyde into amine functionality ( Table 9 , entry 6).…”

Chemoselective Lipase-Catalyzed Synthesis of Amido Derivatives from 5-Hydroxymethylfurfurylamine

“…Nowadays, the use of enzymes is particularly attractive in organic synthesis due to their chemo-, regio-, and stereoselective reactivity under mild reaction conditions. Particularly, straightforward and selective transformations to produce HMF derivatives have been extensively studied in the last decade. − Thus, a vast number of biocatalysts have been identified for the production of various HMF derivatives such as oxidases, alcohol dehydrogenases, amine transaminases, − and reductive aminases …”