A palladium-catalyzed stereospecific and regioselective cross-coupling of enantiopure 2-arylaziridines with arylboronic acids under mild conditions to construct a tertiary stereogenic center has been developed. N-heterocyclic carbene (NHC) ligands efficiently promote the coupling, suppressing beta-hydride elimination. The enantiospecific cross-coupling allowed us for preparation of a series of biologically important 2-arylphenethylamine derivatives in an enantiopure form.