Regio- and Stereoselective β-Sulfonylamination of Alkynes via Photosensitized Bifunctional N–S Bond Homolysis

Nitrogen central radicals (NCRs) are versatile synthetic intermediates for creating functional nitrogen-containing molecules. Herein, a photosensitized β-sulfonylamination of terminal alkynes as well as acetylene has been established by employing <i>N</i>-sulfonyl heteroaromatics as bifunctional reagents (BFRs) to efficiently deliver versatile (<i>E</i>)-β-sulfonylvinylamines with excellent regio- and stereoselectivities. Mechanistic studies suggest a base-accelerated energy transfer (EnT) photocatalysis involving aromatic NCR formation, radical addition to alkynes, and sulfonylation processes.