Abstract Tin-free radical reactions based on α-scission of alkylsulfonyl radicals are very useful for the formation of carbon–carbon bonds and include allylation, acylation, cyanation, vinylation, and carbonylation. For secondary, tertiary, and benzylic radicals, it is possible to use the corresponding iodides as precursors but the primary radicals still require the use of phenyl tellurides or alkyl allyl sulfones. Especially, alkyl allyl sulfones are highly efficient and most reliable primary alkyl radical precursors for the further formation of carbon–carbon bonds. The present approach is very useful for introducing various functional groups such as carbonyl and alkenyl groups under tin-free conditions.