Anode Material Determined Divergent 5‐<i>exo‐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.