One‐Pot Amidation/C─H Halogenation by an Efficient Electrochemical Cascade

ABSTRACT The advancement of sustainable synthetic methodologies is a central goal of modern chemistry, given the societal importance of green chemical practices. Amide groups and halogen atoms are prevalent in chemical and biological systems, with major relevance to both organic and medicinal chemistry. Consequently, there is strong demand for efficient methods that enable amide bond formation and selective halogenation under mild, resource‐efficient conditions. Conventional approaches typically require separate steps, activating reagents, catalysts, or harsh reaction conditions, which limit scalability and sustainability. To address these challenges, we developed a novel electrochemical cascade methodology that unites amide bond formation and electro‐induced C─H halogenation in a single, atom‐economical, and environmentally benign process. This strategy provides streamlined access to halogenated N ‐aryl amides, carbamates, and ureas without additives or co‐reagents. The method's generality and robustness are demonstrated across more than 145 examples, encompassing complex, functional group‐dense scaffolds and pharmaceutically relevant compounds, including successful scale‐up reactions.