The Rh-DuPHOS and Rh-BPE catalyzed hydrogenation of β-substituted α,β,γ,δ-unsaturated amino acids establishes two contiguous stereogenic centers simultaneously. Both high regioselectivity and good to excellent enantioselectivity have been demonstrated in this process leading to β-branched allyl glycine derivatives. Enamide geometry was found to influence stereoselectivity. Studies aimed at defining the scope and limitations of this process are described.