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This review provides an overview of the recent progress made in the area of free-radical additions across the ?-system of olefins, with a focus on the role of sulfonyl derivatives as one of the reaction partners in multicomponent processes. The mechanism and utility in organic synthesis of carbo-alkenylation, alkynylation, oximation and azidation of olefins are thus discussed and illustrated with some applications in total synthesis of natural products.