Electrochemical Amino‐Oxygenation Cyclization via Alkene Radical Cation/Bisnucleophile Engagement to Saturated <i>N</i>/<i>O</i>‐Heterocycles

Regioselective functionalization of alkenes to create nitrogen- and oxygen-containing heterocycles remains a significant challenge in organic synthesis. Because of their unique electronic and biological properties, these heterocycles are crucial in pharmaceuticals and materials. Herein, we present an electrochemical amino-oxygenation of alkenes using alkene radical cations and bisnucleophiles, enabling the synthesis of saturated N/O-heterocycles in an undivided cell. This method employs readily available amides and alkenes, eliminating the need for additional oxidants or redox catalysts. The in situ generation of alkene radical cations results in high yields with excellent regio- and chemoselectivity. Our approach offers a direct route to six-, seven-, and eight-membered N/O-heterocycles from simple starting materials, broadening access to complex molecules essential for medicinal chemistry and materials science.