Photoredox‐Catalyzed Metal‐Free Regio‐ & Stereoselective C(sp2)–H Amination of Enamides with N‐Aminopyridium Salts

Comprehensive Summary A visible‐light‐induced photoredox‐catalyzed regioselective and stereoselective C(sp 2 )–H amination of enamides with bench‐stable and easily accessible N ‐aminopyridium salts is developed, affording synthetically and biologically prominent vicinal 1,2‐diamine scaffolds with broad substrate scope and excellent functional group compatibility. The transformation proceeded through a radical pathway involving the Giese addition of the relatively electrophilic N ‐centered sulfonamidyl radical species to nucleophilic β‐olefinic position of enamides followed by the ensuing single electron oxidation and β‐H elimination, delivering geometrically‐defined Z ‐configured β‐sulfonamidylated enamides. The operational simplicity, environmental friendliness and cost efficiency of this methodology allowed it to pave a new avenue to enrich the arsenal of synthetically crucial functionalized enamides and their related derivatives.