Trisulfur-Radical-Anion-Triggered C(sp)-H Amination of Electron-Deficient Alkenes

A trisulfur-radical-anion (Ṡ)-triggered C(sp)-H amination of α,β-unsaturated carbonyl derivatives with simple amines has been demonstrated. This protocol provides convenient access to a variety of synthetically valuable N-unprotected and secondary β-enaminones with absolute Z selectivity and tertiary β-enaminones with E selectivity. Mechanistic probe and electronic structure theory calculations suggest that Ṡ initiates the nucleophilic attacks via a thiirane intermediate.