A Catalytic Method to Activate Nitromethane by the Cooperation of Homo‐ and Heterogeneous Catalysis

The achievement of directly activating and utilizing bulk small molecules has remained a longstanding objective in the field of chemical synthesis. The present work reports a catalytic activation method for bulk chemical nitromethane (MeNO2). This method combines homogeneous Lewis acid with recyclable heterogeneous Brønsted acid catalysis, featuring practicality, sustainability, and low cost, thus solving the inherent drawbacks of previous Nef processes where stoichiometric reductants or activators were required. By combining the advantages of both homo‐ and hetero‐geneous catalysts, this chemistry may not only offer new opportunities for the further development of MeNO2 as a nitrogen source for organic synthesis, but also promote the catalysis design in synthetic chemistry.