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An unprecedented set of efficient, economical, atom-economic and exceedingly selective I2–DMSO-promoted methods is described for the generation of different structures. The reaction represents the first of its kind, involving the use of different iodine concentrations, temperatures, acids and salt to adjust the selectivity for the synthesis of different alkenes, α-functionalized ketones and α-ketomethylthioesters.

Graphical abstract: Iodine–DMSO-promoted divergent reactivities of arylacetylenes

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