Manganese catalyzed transfer hydrogenation of biomass-derived aldehydes: Insights to the catalytic performance and mechanism

Manganese catalyzed transfer hydrogenation (CTH) of aldehydes is an attractive method for the synthesis of alcohols. Here, we report a novel and efficient MnO@C-N catalyst for the CTH of biomass-derived 5-hydroxymethylfurfural and other aldehydes to alcohols in high yields. Catalytic experimental studies showed that the MnO and nitrogen-doping are responsible for the high selectivity and high conversion, respectively. Isotopic labelling experiments demonstrated that the CTH of aldehydes to alcohols over MnO@C-N is via a route by direct hydrogen transfer . Kinetic studies revealed that the N-doping can improve the reaction rate and reduce the activation energy of the aldehydes conversion. DFT calculations also indicated that both pyridine N and pyrrolic N doping can reduce the energy barrier for acetone desorption by the interaction between N and hydroxyl-H of alcohol. Furthermore, MnO@C-N showed good recyclability for at least five reaction cycles. We anticipate that these results can drive progress in the manganese catalyzed transfer hydrogenation reaction.