Hydrogenation‐rearrangement of furfural into cyclopentanone or cyclopentanol: Intrinsic behavior on Cu–M systems

Abstract Furfural upgrading to downstream value‐added chemicals represents a pivotal transformation in biomass valorization. In this work, we focus on the hydrogenation‐rearrangement of furfural to produce either cyclopentanone (CPO) or cyclopentanol (CPL), both of which were reported to be very difficult to synthesize with high yield. We report a strategy for the targeted activation of the furanic C–O–C bond using deliberately designed Cu–M/Al 2 O 3 (M = Co, Fe, etc.) systems. Integrated experimental and computational studies reveal that distinct Cu–M–O x interfaces originating from the Cu 2 CoO 3 phase govern the adsorption behavior of furan derivatives. This structure simultaneously retards Cu reduction, generates Brønsted acid sites, and enhances the reaction kinetics. In contrast to the arrested reaction over Cu–Fe/Al 2 O 3 that affords an 89.6% yield of semi‐hydrogenated CPO, the Cu–Co–O x interface enables direct regulation of the reactant adsorption configuration, delivering a remarkable 92.3% yield of CPL.