Biomimetic oxygen activation and electron transfer for aerobic oxidative 5-hydroxymethylfurfural to 2,5-diformylfuran

2,5-diformylfuran (DFF) is a key near-market platform chemical that has been widely used to synthesize various useful compounds. In this study, a unique biomimetic system was developed by splitting the oxidation process into multi-step redox circulations, which can increase markedly the activity and selectivity for the aerobic oxidation 5-hydroxymethylfurfural (HMF) to DFF. An Anderson-type catalyst CeCu(OH)6Mo6O18, with similar properties to oxygenase enzymes, was prepared by the ion exchange method, in which the cation Ce4+ species was employed as electron transfer mediators (ETMs) as well as the anion [Cu(OH)6Mo6O18]4− was used as the electron-donor. The Mo5+ and Ce4+ species on the surface of the catalyst play very important roles in the oxidation process of HMF to DFF. The aerobic oxidation of HMF over the CeCu(OH)6Mo6O18 catalyst could bring out DFF with a yield of 99% in p-chlorotoluene. It provides a promising and highly environmentally friendly approach for the aerobic oxidation HMF to DFF.