We have recently shown that biobased furanic diols can serve as potential replacements for bisphenol A (BPA). Unlike BPA, several of the furanic diols prepared from 5-hyrdoxymethyl furfural (HMF) and 2,5-diformylfuran (DFF) show no estrogenic activity and thus have the potential to be safe BPA alternatives.  In our previous work, the furanic diols were synthesized using pyrophoric Grignard reagents. In order to develop a greener and safer synthetic method, we have investigated Barbier reactions of HMF, DFF, and other furan dialdehydes using bismuth and zinc as metals and reactive halides under aqueous conditions. These reactions proceed in high yields with a variety of allyl halides and are very convenient to scaleup. Selective reaction of dialdehydes with nucleophiles to synthesize unsymmetrical diols is an unsolved problem.  We have developed a protocol for the synthesis of unsymmetrical diols from dialdehydes using a sequential reaction with bismuth and zinc as metals under Barbier conditions.  These are the first examples of selective functionalization of dialdehydes using Barbier reactions.  Details of these novel reactions will be presented.

Barbier reactions: Synthesis of unsymmetrical diols from dialdehydes under aqueous conditions

ACS Spring 2022

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