Neighboring π‑Amide Participation in Thioether Oxidation: Conformational Control

The electrochemical oxidation of thioethers is shown to be facilitated by neighboring amide participation. ¹H NMR spectroscopic analysis in acetonitrile solution of two conformationally constrained compounds with such facilitation shows that two-electron participation by the amide π₂ orbital can occur to stabilize the developing sulfur radical cation.