Highly reactive iodoalkenes (α-iodostyrene and α,α′-diiodo-1,4-divinylbenzene) were prepared and used as substrates in palladium-catalysed aminocarbonylation reaction. Regardless of the type of amine nucleophile the corresponding N-substituted phenylacrylamides have been formed chemoselectively in nearly quantitative yields. High isolated yields (up to 83%) have been achieved both with unfunctionalised simple amines and amino acid methyl esters under mild reaction conditions.