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

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.