Mn–porphyrin-based supramolecular framework catalyst for Mukaiyama-type epoxidation

Molecule-based heterogeneous catalysts are appealing due to their ability to combine the durability and recyclability of heterogeneous catalysts and the structural tunability of molecule-based homogeneous catalysts. Based on our original concept of supramolecular framework catalysts, we develop a new Mn–porphyrin-based supramolecular framework catalyst ( [MnBPPy] FC ) formed through intermolecular interactions. This catalyst facilitates the Mukaiyama-type epoxidation of alkenes using molecular oxygen as an eco-friendly oxidant under ambient conditions. In comparison to our previously described Ru–porphyrin-based supramolecular framework catalyst ( [RuBPPy] FC ), [MnBPPy] FC demonstrates significantly improved catalytic activity and sustainability by utilizing a metal center that is earth-abundant and environmentally friendly. Additionally, the turnover frequency and production rate of [MnBPPy] FC for styrene oxide under mild conditions surpass those of previously documented porous crystalline frameworks with earth-abundant metal centers. These findings underscore a promising approach for developing sustainable and effective molecule-based heterogeneous catalysts for epoxidation. • Mn–porphyrin-based supramolecular framework catalyst promotes aerobic epoxidation. • The framework catalyzed the reaction under environmentally friendly conditions. • Mn-based framework exhibited superior catalytic activity compared to its Ru analogue. • Highest production rate of styrene oxide among relevant systems was achieved.