Electrochemical Radical‐Polar Crossover Enabled Multi‐ester Functionalized <i>O</i>‐Containing Heterocycles Synthesis

Abstract We report an electrochemical radical‐polar crossover (RPC) strategy for the radical cyclization of olefinic amides with C−H nucleophiles with H 2 as the byproduct. Enabled by this strategy, structurally diverse multi‐ester functionalized benzoxazines and iminoisobenzofurans were obtained with good yields. Notably, the resulting triple‐ester functionalized O ‐heterocycles are inaccessible by other means. This protocol features catalyst‐ and external oxidant‐free conditions, high atom economy, and broad substrate scope. The scalable synthesis as well as product derivatization highlight the synthetic utility of this electrochemical protocol.