Light‐Driven Distal Difunctionalization of Thioalkynes Using Thiosulfonates as Bifunctional Reagents

A site‐selective light‐driven 1,4−thiosulfonylation of thioalkynes with thiosulfonates as bifunctional reagents was developed. Through a radical cascade, a panel of difunctionalized compounds has been synthesized with a complete regio‐ and diastereoselectivity for Z ‐isomers (19 examples, up to 67% yield). Mechanistic studies suggested that the reaction occurred via an E n T process.