Cobalt disulfide promotes the selective rearrangement–hydrodeoxygenation of furan alcohols to cyclopentenones

• DOI: 10.1002/aic.18819
• Publication Date: 2025-03-15T07:10:30Z
• Authors: Miao Ding; Xiang Li; Zhijun Xie; Jun Wang; Junjian Xie; Ji‐Jun Zou; Qiang Deng

AbstractDeveloping an efficient catalyst for converting furan alcohols to cyclopentenones for fine chemical synthesis is crucial but challenging due to the easy overhydrogenation side reactions to tetrahydrofuran alcohols and cyclopentanones. This study demonstrates that cobalt disulfide (CoS2) exhibits an unprecedented yield of 80.1% during rearrangement–hydrodeoxygenation of furan alcohol to cyclopentenone. CoS2 acts not only as the Lewis acid sites for the rearrangement step but also as adjustable H2 activation sites for the CC hydrogenation of 4‐hydroxy‐2‐cyclopentenone intermediates, promoting the efficient synthesis of cyclopentenone. Furthermore, it exhibits, for the first time, a similar synthesis route toward 3‐methyl cyclopentenone from 5‐methyl furan alcohol and 2,5‐dihydroxymethyl furan. In addition, we further explored the high‐value utilization of cyclopentenones to high‐density fuels with densities of 0.904–0.908 g/mL via self‐photosensitized [2 + 2] cycloaddition and subsequent hydrodeoxygenation. This study presents the green and efficient synthesis of two cyclopentenones and a way for their high‐value utilization as high‐density fuels.