Nickel-catalyzed intelligent reductive transformation of the aldehyde group using hydrogen

Abstract

The selective transformation of the aldehyde group (–CHO) in multifunctional oxygenates is a key challenge in the development of sustainable biomass feedstock. Herein, a smart Ni-MFC catalyst was developed from a 2D Ni-based metal–organic framework (MOF), which efficiently promoted the transformation of –CHO in the presence of H₂ to a methyl group (–CH₃) via the reductive etherification and hydrogenolysis of the C–O ether bond in methanol. Moreover, the catalytic process could be controlled to directionally produce methyl ether (–CH₂OR) using the reductive etherification protocol. For the catalytic reduction of vanillin, the Ni-MFC-700 catalyst guaranteed the full conversion of vanillin and 96.5% yield of the desired 2-methoxy-4-methylphenol (MMP), while the Ni-MFC-500 catalyst afforded about 82.7% yield of 4-(methoxymethyl)-2-methoxyphenol in methanol solvent. This is a novel and promising approach for the valorization of multifunctional oxygenates and biomass-derived platform compounds.