Here, the highly enantioselective construction of 3,3-disubstituted tetrahydropyridines via Pd(0)-catalyzed asymmetric vinylborylation of (Z)-1-iodo-dienes and B₂pin₂ in the presence of a (S)-p-CF₃-BnPHOX ligand is reported. This process is supposed to be initiated by oxidative addition of Pd(0) to vinyl iodide, followed by transmetallation with B₂pin₂, insertion of the pendant alkene and reductive elimination of alkyl–Pd(II)-Bpin.