Access to Polysulfides through Photocatalyzed Dithiosulfonylation

Abstract In this study, we outline a general method for photocatalyzed difunctionalization of alkenes, a diene, alkynes, 1,3‐enynes, and [1.1.1]propellane using dithiosulfonate reagents (ArSO 2 ‐SSR) with improved atom economy. Both “ArSO 2 ‐” and “‐SSR” on the dithiosulfonate are transferred under mild conditions with broad substrate scope, high stereoselectivity, and complete regioselectivity. Significantly, the resulting dithiosulfonylated styrene is a general and practical nucleophilic disulfuration reagent, reacting with a variety of electrophiles efficiently. Both reactions can be conducted on gram scale, rendering the approach highly valuable.