Photoinduced, Energy-Transfer-Mediated Synergistic N,S-Difunctionalization of Alkenes with CN Migration

A synergistic strategy by merging N,S-difunctionalization of alkenes with CN migration was successfully accomplished by virtue of the newly designed bifunctional reagent bearing the SCN functionality. This protocol exhibits a broad substrate scope for alkenes with tunable alkyl chains, and the corresponding cyanoalkyl β-aminosulfide derivatives were successfully obtained in moderate to high yields. The facile 1,4- and 1,5-CN relocations via intramolecular radical rearrangement allow simultaneous access to remote functionalization and difunctionalization of alkenes with controllable reactivities. Under simple, mild, and easily achievable conditions, this protocol unlocks new synthetic routes to densely functionalized molecules with a high degree of structural diversity.