Oxygen Vacancies in β-MoO <sub>3</sub> Mediate Imine Synthesis via Reductive Coupling of Nitro Compounds and Alcohols
Ziliang Yuan, Yijing Gao, Qingjie Tang, Jianguo Wang, Xun Li, Zehui Zhang
Abstract
Organonitrogen chemicals with C=N bonds are one of the most important groups of chemicals with broad applications, but their synthesis via reductive coupling remains a great challenge, because of the favorable hydrogenation of C=N bonds into C–N bonds. In this study, a nitrogen-doped carbon-supported β-MoO 3 catalyst with abundant oxygen vacancies (O v ) was discovered to be robust in the reductive coupling of nitro compounds with biomass-derived alcohols toward the synthesis of organonitrogen chemicals, including imines and N -heterocycles with C=N bonds. The O v in β-MoO 3 serves a crucial role in the adsorption and activation of substrates via the electronic interaction between the negatively charged oxygen atoms in these substrates and the O v sites in β-MoO 3 . The presence of O v greatly lowers the energy barriers of the reductive coupling reaction, and the electron transfer from alcohols to nitro compounds is mediated by the Mo 5+ /Mo 6+ redox cycle. Our method demonstrates excellent selectivity to C=N bonds and is effective for a wide substrate scope including the highly inert methanol and ethanol. This study highlights the use of non-noble metal oxides as alternatives to traditional metal nanoparticles for various challenging organic transformations.