Key points are not available for this paper at this time.
Reductive-coupling of nitro compounds and alcohols is a sustainable route for constructing C = N bonds in organonitrogen chemicals, yet challenging due to the inertness of α-Csp3-H bond in alcohols and the vulnerability of C = N bonds towards hydrogenation. Here, we report the surprising catalytic activity of ultrafine alkaline-earth metal oxide MgO nanoclusters (0.9 ± 0.3 nm) that efficiently activate α-Csp3-H bonds, facilitating the transfer hydrogenation and synthesis of value-added chemicals bearing C = N bonds with high to excellent yields (86–99%). Controlled experiments and characterizations showed the crucial role of oxygen vacancies (Ov) and local Mg environment (Mg-O bond) in MgO for substrate adsorption and activation via electronic interactions between substrate’s negatively charged oxygen atoms and Ov sites in MgO nanoclusters. Theoretical calculation further confirmed that Ov significantly lowered the energy barrier of the hydrogen atom transfer from α-Csp3-H in ethanol to the nitro group in nitrobenzene (29.3 vs. 52.9 kcal/mol), which is the rate-determining step with the highest energy barrier in reductive-coupling reactions. Our method not only provides an efficient and sustainable pathway for synthesizing organonitrogen chemicals with C = N bonds but also inspires the exploration of main group element catalysts as alternatives to transition metal and noble metal catalysts for organic transformations. The reductive coupling of alcohols and nitro compounds typically yields amine products. Here the authors show that MgO nanoclusters catalyse this reaction, giving unsaturated C = N containing products.
Yuan et al. (Wed,) studied this question.