Electrochemical C7‐Indole Alkenylation via Rhodium Catalysis

Abstract Indole derivatives are fundamental structural units in many bioactive compounds and molecular materials. The site‐selective C7‐functionalization of these moieties has been proven to be extremely challenging due to the inherent reactivity of the C2‐ and C3‐positions. Herein, we report the first electro‐C7‐alkenylation of indoles. This novel and sustainable methodology provides highly exclusive access to the C7‐position devoid of often toxic and expensive chemical oxidants. Moreover, an array of substrates was successfully alkenylated at the C7‐position, and versatile product diversification was achieved.