Copper‐Catalyzed Radical Cross‐Coupling of Oxime Esters and Sulfinates for Synthesis of Cyanoalkylated Sulfones

Abstract Sulfones and alkylnitriles play a significant role in both organic and medicinal chemistry, as versatile synthetic building blocks and privileged pharmacophores in many natural products and bioactive compounds. Herein, a room‐temperature, copper‐catalyzed radical cross‐coupling of redox‐active cycloketone oxime esters and sulfinate salts is described for the first time. Key to the success of this process involves catalytic generation of a cyclic iminyl radical and ensuing ring‐opening C−C bond cleavage. The resultant cyanoalkyl radical is then engaged in cross‐coupling with nucleophilic sulfinate to form cyanoalkylated sulfones.