Cu catalyzed oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran and 2,5-furandicarboxylic acid under benign reaction conditions

The renewable chemical building block 5-hydroxymethylfurfural (HMF) was oxidized to 2,5-diformylfuran by an oxidation system consisting of the radical 2,2,6,6-tetramethyl-piperidin-1-oxyl (TEMPO) and CuCl. The system was optimized by exploring several reaction conditions and by employing nitrogen containing promoters (NCPs) to obtain excellent yields. In acetonitrile a 95% DFF yield was obtained after 24 h with ambient pressure of dioxygen at room temperature in the presence of different NCPs, which – to our knowledge – is the best result reported thus far for this reaction. The use of NCPs made it further possible to apply various traditional solvents, e.g. acetone, methanol and methyl isobutyl ketone for the reaction. The latter can be used as extraction solvent for HMF synthesis in aqueous media and thus integrate the two processes. Additionally, HMF was oxidized to 2,5-furandicarboxylic acid by a modified oxidation protocol consisting of CuCl and t-BuOOH. In all the reactions, mild conditions, including room temperature were employed.

Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (125 K)Download as PowerPoint slideHighlights► Aerobic oxidation of HMF to DFF was performed at ambient conditions with CuCl/TEMPO. ► An optimized DFF yield of 95% was obtained with use of nitrogen containing promoters. ► HMF was oxidized directly to FDA by oxidation with CuCl/t-BuOOH catalyst.