Iron-based single-atom catalysts for selective ammoxidation of C(sp³)–H bonds and oxidative C–C cleavage reactions

Ammoxidation of methylarenes using ammonia and air is the main method for the synthesis of aromatic nitriles in the chemical industry. Despite significant efforts in industry and academia, no general and selective catalyst based on less toxic and earth-abundant metals has been developed for this reaction. Here we report a single-atom iron-based material (Fe@BNC-800-L1) with Fe–N₅–B_x configuration as an efficient sp³-hybridized C–H- and C–C bond oxidation catalyst. Due to the presence of Fe³⁺, B and N species, which are co-embedded in the micro-mesoporous carbon matrix, these materials show excellent activity for ammoxidation of methyl-substituted (hetero)arenes. Furthermore, highly selective C–C bond cleavage reactions of alkylarenes are presented, which complement the toolbox for nitrile synthesis. The generality of this presented Fe-based ammoxidation methodology is showcased by the straightforward and selective synthesis of >60 functionalized and structurally diverse nitriles, which are important precursors and key intermediates in organic synthesis with many applications in life sciences and industry.