A palladium(II)-catalyzed vicinal as well as geminal selective dicarbofunctionalization of allylamine embedded in a removable picolinamide auxiliary is developed by exploiting nucleopalladation triggered intermolecular three-component coupling reaction. The vicinal selectivity was accomplished by engaging allylamine, indoles, and aryl or styrenyl halides through a Pd(II)/Pd(IV) reaction manifold, while the two-fold coupling... Show more