A palladium-catalyzed alkyne insertion/Suzuki reaction with unactivated alkyl iodides is described. Under the reaction conditions, selective migratory insertion of alkynes avoids beta-hydride elimination and provides a facile synthesis of stereodefined, tetrasubstituted olefins. The transformation offers broad substrate scope for both the alkyl iodide and boron nucleophile. Mechanistic studies have revealed inversion of the stereocenter for the carbon bearing the iodide.