Electrochemical Cascade N ‐Acylation and C–H Halogenation of Azaindoles

The development of synthetic methods that enable the conversion of readily accessible chemicals into highly valuable small organic molecules, especially those with potential pharmacological and medicinal applications, holds substantial importance in organic synthesis. In this regard, the synthesis of substituted azaindoles and their derivatives, given their structural diversity, presents a considerable synthetic challenge. Herein, we report the development of a novel electrochemical cascade methodology that unites amide bond formation and electro‐induced C–H halogenation of azaindoles in a single, atom‐economical, and environmentally benign process. This approach enables the direct and efficient preparation of halogenated N ‐acyl azaindole amides and carbamates, operating efficiently without the need for additives or supporting electrolytes. Taken together, these results underscore the power of the cascade strategy and its promise for broad application in the exploration of uncharted chemical space relevant to biomedical research.