Electrochemical Tandem Self‐Coupling/Selenylation of Acetonitrile toward Highly Functionalized Tetrasubstituted Alkenes

Herein, an electrochemical tandem reaction that integrates acetonitrile self‐coupling with selenylation to construct densely functionalized tetrasubstituted alkenes bearing amino, cyano, and seleno groups from readily available acetonitrile and diselenides is reported. Employing potassium iodide as a redox mediator under mild, metal‐free, and oxidant‐free conditions, this sustainable strategy leverages the synergistic effect of electrochemical oxidation and iodine catalysis to achieve inert C( sp 3 )H bond activation of acetonitrile. The transformation exhibits good stereoselectivity along with substrate scope across diverse aryl and alkyl selenides.