Electrochemical Oxidative Radical Polar Crossover Route to 1,4‐Keto Carboxylates Mediated by Anchimeric Assistance

The 1,4‐keto carboxylate scaffold is present in the structure of many biologically relevant compounds. To date, there are only a branch of methods to prepare them, using either transition metal catalysts, or non‐commercially available and sensitive starting materials. Herein, we describe a sustainable electrochemical methodology starting from commercially available and highly stable 1,3‐diketones and alkenes to prepare 1,4‐keto aryl and alkyl carboxylates in a highly efficient manner, without the need of an external catalyst or harsh reaction conditions. This electrochemical oxidative radical polar crossover transformation presents a broad scope, is compatible with many functional groups, and can even be applied in flow chemistry. In addition, the key stabilization of the intermediate carbocation by anchimeric assistance allows a high diastereo‐ and regio‐control of the reaction. Moreover, the utility of these 1,4‐keto carboxylates was demonstrated in several derivatizations and applications in the late‐stage functionalization of bioactive compounds.