Superelectrophilic activation of 5-hydroxymethylfurfural and 2,5-diformylfuran: organic synthesis based on biomass-derived products

Abstract

SummaryThe reaction of 5-hydroxymethylfurfural (5-HMF) with arenes in superacidic trifluoromethanesulfonic acid (triflic acid, TfOH) as the solvent at room temperature for 1–24 h gives rise to 5-arylmethylfurfurals (yields of 17–91%) and 2-arylmethyl-5-(diarylmethyl)furans (yields of 10–37%). The formation of these two types of reaction products depends on the nucleophilicity of the arene. The same reactions under the action of acidic zeolites H-USY in high pressure tubes at 130 °C for 1 h result in the formation of only 5-arylmethylfurfurals (yields of 45–79%). 2,5-Diformylfuran (2,5-DFF) in the reaction with arenes under the action of AlBr3 at room temperature for 1 h leads to 5-(diarylmethyl)furfurals (yields of 51–90%). The reactive protonated species of 5-HMF and 2,5-DFF were characterized by NMR spectroscopy in TfOH and studied by DFT calculations. These reactions show possibilities of organic synthesis based on biomass-derived 5-HMF and 2,5-DFF.

Synthetic Study of 5‐Hydroxymethylfurfural in Groebke‐Blackburn‐Bienaymé Reaction

“…The high degree degradation observed under these conditions could be attributed to the limited stability of 5‐HMF under high temperatures and strong acid medium reactions [10,12] . This reactivity could also carry over to the hydroxymethyl functionality or furan ring in the GBB product with the concomitant formation of dimerization and oligomerization reactions, generating shortcomings in terms of lower yields and side‐reactions [46,47] . In this context, we selected milder conditions to continue with the next experiments.…”

“…[10,12] This reactivity could also carry over to the hydroxymethyl functionality or furan ring in the GBB product with the concomitant formation of dimerization and oligomerization reactions, generating shortcomings in terms of lower yields and sidereactions. [46,47] In this context, we selected milder conditions to continue with the next experiments. Based on Demjén et al work in a GBB-3CR under mild conditions; ethanol was used as green solvent along with a catalytic amount of TFA (20 mol %).…”

5-Hydroxymethylfurfural (HMF) in Organic Synthesis: A Review of its Recent Applications Towards Fine Chemicals

“…[164] Recently, Vasilyev and coworkers reported the arylation of HMF with arenes in trifluoromethanesulfonic acid medium at room temperature. [165] 5-Arylmethylfurfurals 143 were prepared in 17-91% yields, along with by-products 2-arylmethyl-5-(diarylmethyl)furans 144 (5-37% yield) when highly nucleophilic arenes were used. Increasing the reaction time significantly affected the yield of the by-product.…”

Expanding the biomass derived chemical space

“…Whereas reaction of HMF with benzene exclusively afforded the phenylmethyl furfural and kept the aldehyde group of furfural intact, similar reactions with more activated arenes such as toluene, xylenes, mesitylene and anisol afforded higher substituted Friedel Crafts products ( Scheme 4 ). 45 The formed arylated furans may be used to access bioactive compounds such as antibiotics. 46 …”