Anode material determined divergent 5‐<i>exo</i>‐<i>dig</i> cyclization of <i>N</i>‐cyano‐2‐halobenzamides toward 3‐iminoisoindolin‐1‐ones and 3‐aminoisoindolin‐1‐ones

Abstract Herein, an electroreductive aryl radical enabled 5‐ exo ‐ dig cyclization of N ‐cyano‐2‐halobenzamides is presented, providing a convenient route for the synthesis of a variety of 3‐iminoisoindolin‐1‐ones in 30–75% yields. Simply by employing zinc plate instead of graphite rod anode, the products of the electrosynthesis are switched to diverse 3‐aminoisoindolin‐1‐ones through aryl‐radical‐mediated 5‐ exo ‐ dig cyclization and subsequent reductive hydrogenation. Furthermore, this anode material determined divergent 5‐ exo ‐ dig cyclization features mild electrochemical conditions, excellent substrate scopes, and good functional group tolerance.