The chiral short-bite ligands (R_a,R_a)-bis(dinaphthylphosphonito)methane, (R_a,R_a)-1, (R_a,R_a)-bis-dinaphthylpyrophosphite, (R_a,R_a)-2, (S_c)-bis(diphenylphosphino)-sec-butylamine, (S_c)-3, (R_a,R_a)-bis(dinaphthylphosphonito)phenylamine, (R_a,R_a)-4a, (R_a,R_a,S_c)-bis(dinaphthylphosphonito)-sec-butylamine, (R_a,R_a,S_c)-4b, and (R_a,S_c)-(dinaphthylphosphonito)(diphenylphosphino)-sec-butylamine, (R_a,S_c)-5, have been synthesised. The cationic palladium–allyl mononuclear chelate, [Pd(η³-PhCHCHCHPh)(μ-L–L_short-bite)]PF₆ [L–L_short-bite = (S_c)-3, (R_a,R_a)-4a, (R_a,R_a,S_c)-4b and (R_a,S_c)-5 for complexes 8, 9, 10 and 11, respectively] and binuclear bridged [Pd(η³-PhCHCHCHPh)(μ-R_a,R_a-2)]₂(PF₆)₂, 12, have been isolated. The short-bite chiral ligands synthesised have been tested in the palladium–allyl catalysed substitution reaction of 1,3-diphenylallyl acetate with dimethyl malonate. The catalytic system was studied, in solution, by a multinuclear NMR technique. In the catalytically active species formed with (R_a,R_a)-2 ligand, [Pd(η³-PhCHCHCHPh)(R_a,R_a-2)]₂(PF₆)₂, 12, the palladium(II) centres are bridged by two ligands which are forced to adopt a nearly cis-coordination to allow coordination of the allyl-moiety. Semiempirical calculations on a biphenyl-model molecule, similar to the species 12, indicate that this situation induces a strain and rigid conformation in the chiral ligands, which produce differences in the terminal allyl carbon atoms. As consequence, the catalytic product was obtained with an enantiomeric excess of 57.1% in the S form. A low e.e. value was obtained when the (R_a,R_a)-1, (S_c)-3, (R_a,R_a)-4a, (R_a,R_a,S_c)-4b and (R_a,S_c)-5 ligands have been tested in the same palladium-catalysed reaction.