Photoredox Regioselective Thioesterification/Disulfuration of Alkenes

Disulfides and thioethers are important motifs in medicinal and agrochemical chemistry; however, the regioselective incorporation of distinct sulfur functional groups remains challenging because of the comparable reactivities of sulfur-centered radicals. Herein, we report a photocatalytic thioesterification/disulfuration of alkenes using tetrasulfides and acyl disulfides with broad scope and high regioselectivity. Mechanistic studies reveal that the photosensitive acyl trisulfides are generated and serve as oxidative quenchers of excited photocatalyst to form acylthio radicals and perthiolates, enabling the chemoselective difunctionalization of alkenes.