Hydrogenation Rearrangement of Furan Compounds to Cyclopentanones Catalyzed by CoNC with In Situ‐Generated Uniform Metal–Acid Pairs

The hydrogenation rearrangement of biomass-derived furan aldehydes and ketones to cyclopentanones holds significant promise for sustainable fine chemical production, but developing efficient catalysts with low metal loading and uniform metal-Brønsted sites presents a significant challenge. Herein, we report a CoNC catalyst with in situ generated uniform metal-acid pairs, which exhibits superior activity and selectivity significantly outperforming reported non-noble and noble metal catalysts. Moreover, CoNC shows excellent cycling stability and broad substrate adaptability. Catalyst characterizations, kinetic and isotopic labeling studies reveal that CoNC can efficiently dissociate H₂ to form H⁺-N-Co-H^-, and easily adsorb and activate H₂O for OH^- exchange to form H⁺-N-Co-OH^-, producing abundant Brønsted acid sites that then generate uniform metal-acid pairs. The H₂ activation on the Co site enables the furfural hydrogenation to furfuryl alcohol, and the in situ generated acid sites catalyze the subsequent ring-opening rearrangement. Moreover, the metal-acid pairs effectively suppress undesired side reactions such as over-hydrogenation and polymerization. This work provides a new class of metal-acid bifunctional catalyst and expands the application of M-NC catalysts.