Recent advances in the conversion of furfural into bio-chemicals through chemo- and bio-catalysis

Abstract

Furfural is a promising renewable platform molecule derived from hemi-cellulose, which can be further converted to fossil fuel alternatives and valuable chemicals due to its highly functionalized molecular structure.

C3−H Silylation of Furfurylimines: Direct Access to a Novel Biobased Versatile Synthetic Platform Derived from Furfural

“…Furthermore, by adapting a reported protocol, [52] treatment of 9E with phenylethynyl bromide gave the expected alkynylated product 21, albeit in a poor 19% yield (Scheme 8b). We then passed to tackle [C3(sp 2 )-Si]-to-[C3(sp 2 )-C(sp 3 )] cross-coupling reactions. As no reaction was observed reacting 9E with allyl bromide under Pd(0) catalysis in the presence of AgF, we directed our attention to copper-based strategies, [53,54] and particularly to the use of Cu-F complexes, known to be able to trigger silicon-to-copper transmetalation.…”

“…These molecules, which are obtained by depolymerization/ cyclodehydration of raw biomasses containing C5-and C6monosaccharides, are two renewable platform molecules of high interest for bulk as well as fine chemistry. [3][4][5][6][7][8][9][10][11] In recent years, organic chemists have investigated and developed new CÀ C bond forming protocols on these molecules to obtain new highly functionalized bio-based chemicals or biofuels. [12] Similarly, the biomass-derived furan rings are found in several drugs -such as ranitidine a well-known anti-ulcer agent -but are exclusively substituted in 2-and/or 5 position.…”

“…In particular, the sustainable production of industry‐relevant chemicals, ranging from biofuels to pharmaceuticals, requires the development of efficient functionalization of furan derivatives such as furfural ( 1 ) and 5‐(hydroxymethyl)furfural (HMF, 2 ). These molecules, which are obtained by depolymerization/cyclodehydration of raw biomasses containing C5‐ and C6‐monosaccharides, are two renewable platform molecules of high interest for bulk as well as fine chemistry [3–11] . In recent years, organic chemists have investigated and developed new C−C bond forming protocols on these molecules to obtain new highly functionalized bio‐based chemicals or biofuels [12] .…”

Selective Synthesis of Levulinic Ester from Furfural Catalyzed by Hierarchical Zeolites

“…This effect suggests that the mesopore creation in the beta zeolite was advantageous in retaining the catalytic activity and in avoiding deactivation. The deactivation of solid acid catalysts mainly occurs through the deposition of polymerization products from furfural called humins, as has been often reported in the literature [9,10,12,20,55]. Thermogravimetric analysis (TGA) was employed to investigate the formation of humins for both of the reused catalysts recovered after the second reaction, as displayed in Figure S2.…”

Highly Controllable Hydrogenative Ring Rearrangement and Complete Hydrogenation Of Biobased Furfurals over Pd/La2B2O7 (B=Ti, Zr, Ce)

“…In exploratory studies, furanic aldehydes (furfural and 5-hydroxymethyl furfural) are commonly devoted to model compounds of hemicelluloses and cellulose-based furan derivatives, respectively. [1][2][3][4][5][6] Due to the highly unsaturated state of furanic aldehydes, hydrotreatment is the most common transformation used to synthesize a wide range of high-value chemicals, including linear alcohols (1,5-pentanediol, 1,2-pentanediol, 1,2,5-pentanetriol, and 1,6-hexanediol), furanic alcohols (2-hydroxymethyl furan and 2,5-dihydroxymethyl furan), methylfurans (2-methylfuran and 2,5-dimethylfuran), tetrahydrofuran alcohols (2,5-dihydroxymethyltetrahydrofuran and 2hydroxymethyltetrahydrofuran), cyclopentanones (3hydroxymethyl cyclopentanone and cyclopentanone), and cyclopentanols (3-hydroxymethyl cyclopentanol and cyclopentanol). [7][8][9][10][11][12][13][14][15][16] Among these fine chemicals, cyclopentanones are important feedstocks for lysine, resins, biofuels, and vitamins, [17][18] and tetrahydrofuran alcohols are widely used as solvents, or building blocks of polyesters, polyethers, and adhesives.…”