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Photocatalyzed alkylsulfonylation of unactivated alkenes using DABCO. (SO2)2 and thianthrenium salts via a distal heteroaryl migration process has been developed, which provides a new means of synthesizing a variety of valuable alkylsulfonyl-substituted compounds. These alkylsulfonyl radicals couple with unactivated alkenes to undergo efficient intermolecular reactions, followed by distal heteroaryl migration. This mild catalytic method is tolerant of functional groups and affords medicinally relevant alkylsulfonylated heterocycles. [ABSTRACT FROM AUTHOR]