One-Pot Deoxygenation of Fructose to Furfuryl Alcohol by Sequential Dehydration and Decarbonylation

Fructose was deoxygenated to furfuryl alcohol (FFA) by tandem dehydration and decarbonylation in one pot over the AlCl3⋅6 H2O/Pd(OAc)2 catalyst combination to give a high FFA yield of 40.6 %. AlCl3⋅6 H2O behaves as an effective Lewis acid to catalyze the dehydration of fructose to 5‐hydroxymethylfurfural (HMF), and subsequently, Pd(OAc)2 catalyzes the removal of a CO moiety from HMF to produce FFA selectively. The hydroxyl group on the HMF intermediate was stabilized by poly(1‐vinyl‐2‐pyrrolidinone) through an intermolecular hydrogen bond, which accelerated the dehydration of fructose and inhibited the hydrogenation of HMF by formic acid. The decarbonylation of HMF was promoted and the unwanted decomposition of fructose was inhibited through the use of 4 Å molecular sieves. This research highlights a “one‐pot” catalytic system to transform renewable carbohydrates into fine chemicals by tandem dehydration and decarbonylation reactions without the separation or purification of HMF. In tandem: The direct synthesis of furfuryl alcohol from fructose over a AlCl3⋅6 H2O/Pd(OAc)2 catalyst demonstrates a “one‐pot” catalytic system to transform renewable carbohydrates into fine chemicals by tandem dehydration and decarbonylation reactions. PVP=Poly(1‐vinyl‐2‐pyrrolidinone).