Transition-Metal-Free Olefinic C-H Azidoalkylthiolation via C(sp3)-S Bond Cleavage of Vinylsulfonium Salts

A transition-metal-free olefinic C-H azidoalkylthiolation protocol was developed through C(sp(3))-S bond cleavage of vinylsulfonium salts with sodium azide in air under aqueous conditions. An interrupted Pummerer/nucleophilc azidoalkylation cascade was developed for such a process. The practicability of the synthetic protocol was demonstrated by scale-up preparation of the azidoalkylthiolated tetrasubstituted alkene products and their transformations to diverse triazole and tetrazole derivatives as well as azidoalkylthio-funtionalized N-heterocyclic compounds. The present synthetic methodology features broad substrate scopes and good functional group tolerance under mild conditions.

Automated summary

A transition-metal-free method was developed for the cleavage of C-H bonds in olefins. By using vinylsulfonium salts and sodium azide, sulfanyl-azidoalkene compounds were synthesized and further transformed into various derivatives.