Chemoenzymatic\nSynthesis of Aromatic Vinyl Monomers\nfrom Biorenewable 5‑Hydroxymethyl-2-Furfural

5-Hydroxymethyl-2-furfural (5-HMF), derived from biomass,\nis a\nversatile precursor for various chemicals, including pharmaceuticals,\nbiofuels, plastics, and polymers. This study focuses on synthesizing\naromatic vinyl monomers from 5-hydroxymethyl-2-vinylfuran (5-HMVF).\nInitial steps involve a high-yield Wittig synthesis from 5-HMF, resulting\nin a 95% yield. Enzymatic synthesis using immobilized CAL-B (iCALB)\nyields 5-HMVF acetate, <i>n</i>-butyrate, and benzoate in\nquantitative yields and demonstrates effective enzyme reuse. An alternative\nTEMPO oxidation route produces 5-vinylfuran-2-carbaldehyde (5-VFA)\nwith a 61% yield, which is further converted to <i>E-</i> and <i>Z-</i>5-vinylfuran-2-carboxime (5-VFO) and subsequently\nto 5-vinylfuran-2-carbonitrile (5-VFN) via chemocatalytic dehydration.\nBiocatalytic dehydration of <i>E-</i> and <i>Z-</i>5-VFO to the corresponding nitriles is performed using different\naldoxime dehydratases (Oxd) in water as a sustainable solvent. Polymerization\nof all monomers yields characterized polymer products analyzed by\nTGA, DSC, SEC, and FTIR spectroscopy.