Abstract
Radical-mediated difunctionalization of alkenes and alkynes represents a powerful and efficient strategy for constructing complex molecular architecture from simple unsaturated precursors. The docking-migration approach, which involves the initial addition of a radical species to an alkene or alkyne followed by intramolecular migration of a functional group, has emerged as a versatile and broadly applicable tactic. This review summarizes the achievements in this rapidly developing area, with a focus on the design of bifunctional reagents that enable the simultaneous incorporation of two functional groups via radical addition and migration cascades. The scope encompasses various migrating groups, including aryl, heteroaryl, alkynyl, oximino, alkenyl, and imino units, and highlights extensions to challenging unactivated alkenes and alkynes. The mechanistic insights, substrate scope, and synthetic applications of these transformations are discussed, underscoring the potential of the radical docking-migration strategy in modern synthetic chemistry.