Combining a catalytic enantioselective reaction with dimerization in a single operation is an efficient way to upgrade the enantiomeric excesses (ee) of the product. Palladium-catalyzed reaction of N-(2-iodophenyl)-N-methyl methacrylamide derivatives with oxadiazole afforded, by a double enantioselective carbopalladation/intermolecular heteroarene C-Halkylation sequence, homodimers in good yields with excellent ee values. The dimer was subsequently elaborated to the monomer in which the linker (oxadiazole) was incorporated into the target product.