Novel chiral aminophosphines, N,N-disubstituted diphenyl(1-amino-2-naphthyl)phosphines 4 were synthesized via nucleophilic aromatic substitution reaction on 1-methoxy-2-(diphenylphosphinoyl)naphthalene (1) by chiral lithium amides 2, followed by reduction of the phosphinoyl function. The new ligands were tested for their efficiency in the palladium-catalyzed allylic substitution of dimethyl malonate with 1,3-diphenyl-2-propenyl acetate and high asymmetric inductions up to 80%ee were observed.