Solvent issues in the Baylis-Hillman reaction of 5-hydroxymethyl furfural (HMF) and 5-glucosyloxymethyl furfural (GMF). Towards no-solvent conditions

Abstract

The possibility to apply solventless conditions for the Baylis-Hillman reaction of 5-hydroxymethyl furfural (HMF) and its glucosylated analog, glucosyloxymethyl furfural (GMF) has been investigated. This study shows that highly functionalized adducts can be obtained in fair to good yields, under the conditions combining the renewability of the substrates, the straightforwardness of the strategy, and the lowered cost and toxicity of the solvent conditions. The issue of the polarity of the furanic substrate is addressed by comparing HMF with furfural and GMF.

Renewable synthesis of novel acrylates from biomass‐derived 5‐substituted‐2‐furaldehydes by Morita‐Baylis‐Hillman reaction

“…The characterization data and spectra are supplied as supplementary information (Figure S1–Figure S67) available with this manuscript. The characterization data of 1(a – c) and 2(a – c) matched with published literature [22,24,29] …”

“…The characterization data of 1(a-c) and 2(a-c) matched with published literature. [22,24,29] Reaction conditions: DABCO (1 eq. ), methyl acrylate (2.5 eq.…”

“…Interestingly, the adducts between HMF or FUR with acrylates have been reported to demonstrate the substrate scope during methodology developments of MBH reaction [22,23] . The MBH adducts of furanics with acrylates have been used as a molecular scaffold to synthesize novel pyran‐3(6H)‐ones that are present in various bioactive natural products [24] .…”

“…Interestingly, the adducts between HMF or FUR with acrylates have been reported to demonstrate the substrate scope during methodology developments of MBH reaction. [22,23] The MBH adducts of furanics with acrylates have been used as a molecular scaffold to synthesize novel pyran-3(6H)-ones that are present in various bioactive natural products. [24] However, the systematic synthesis of the MBH adducts of 5-substituted-2furaldehydes, renewably prepared from biomass-derived hexose sugars and polymeric carbohydrates, has never been attempted.…”