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A novel,rational-designed approach to access various heteroaryl-substituted alkyl thioethers was developed via docking-migration cascade process.By utilizing three components involving alkene,dual-function reagent,and thioetherificating reagent,radical heteroarylalkylation of alkenes followed by thiolation of the alkyl radical intermediates proceeded smoothly,manifesting well compatibility of substrates and cascade transformations.Furthermore,this protocol also features mild conditions,broad substrate scope,and wide product diversity.