A radical-mediated hetaryl functionalization of nonactivated alkenes through distal ipso-migration of O- or S-containing hetaryls was developed. Furyl, benzofuryl, thienyl, and benzothienyl groups showed satisfactory migratory abilities. A variety of heteroatom-centered radicals, including azido, trifluoromethylsulfanyl, and silyl radicals readily trigger the migration cascade, and a new C–heteroatom and C–C bond are concomitantly constructed in the reaction. This method provides an efficient approach to the synthesis of high-valued complex O- or S-hetaryl compounds.

The preparation of functionalized thiaphenalene derivatives is of high synthetic value, yet remains underexplored. Herein, we report an efficient approach for the synthesis of 1-thiaphenalene derivatives through radical cyclization of 1-naphthalenesulfonyl chlorides with alkynes. A variety of 1-thiaphenalene derivatives are readily furnished, otherwise difficult to prepare by present methods. The protocol features mild photocatalytic conditions, broad functional group compatibility and high product diversity.