Trisulfur-Radical-Anion-Triggered C(Sp(2))-H Amination Of Electron-Deficient Alkenes

A trisulfur-radical-anion (S-3(center dot-))-triggered C(sp(2))-H amination of alpha,beta-unsaturated carbonyl derivatives with simple amines has been demonstrated. This protocol provides convenient access to a variety of synthetically valuable N-unprotected and secondary beta-enaminones with absolute Z selectivity and tertiary beta-enaminones with E selectivity. Mechanistic probe and electronic structure theory calculations suggest that S-3(center dot-) initiates the nucleophilic attacks via a thiirane intermediate.