Trisulfur-Radical-Anion-Triggered C(sp2)-H Amination of Electron-Deficient Alkenes.
Khang X NguyenPhuc Hoang PhamThao T NguyenChou-Hsun YangHoai T B PhamTung Thanh NguyenHaobin WangNam Thanh Son PhanPublished in: Organic letters (2020)
A trisulfur-radical-anion (S3̇-)-triggered C(sp2)-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 S3̇- initiates the nucleophilic attacks via a thiirane intermediate.