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Radical‐mediated difunctionalization of alkenes provides a promising approach to introduce one alkenyl or alkynyl group to target compounds. However, simultaneous installation of two unsaturated C−C bonds via alkene difunctionalization remains elusive, attributable to the high instability and transient lifetimes of alkenyl and alkynyl radicals. Herein, we report the photocatalytic 1,2‐alkynylalkenylation and 1,2‐enynylalkenylation of alkenes for the first time, triggered by the intermolecular addition of a stabilized allenyl radical to an alkene. A portfolio of strategically designed, easily accessible dual‐function reagents are applied to a radical docking‐migration cascade. The protocol has broad substrate scope and efficiently increases the degree of unsaturation. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]