Six-membered chelate complexes of type Pd(1a-e)Cl2 (2a-e) and Pd(1a-e)(η3-PhCHCHCHPh)BF4 (3a-e) of a series of systematically varied chiral phosphine-amine ligands (S,S)-Ph2PCH(CH3)CH2CH(CH3)NHR 1a-e (R = benzyl 1a, R = ethyl 1b, R = (S)-α-phenylethyl 1c, R = isopropyl 1d, R = methyl 1e) have been studied. The complexes 2a-e were characterized by X-ray crystallography, DFT analysis and in solution by 1D and 2D NMR spectroscopy. A very good correlation has been observed between the steric demand of the N-substituent and the distortion of the chelate. Furthermore, it has been proved that sterically more demanding N-substituents are capable of distorting the chelate to a larger extent along one single, well defined conformational pathway. The careful variation of the N-substituent thus allows a precise stereochemical fine tuning of the metal's coordination sphere. As a substantiation of this concept, the investigation of complexes 3a-e revealed that the exo/endo ratio as well as the twisting of the allyl moiety around the Pd-allyl axis can easily be modified by the proper choice of the nitrogen substituent. Furthermore, Pd-catalysts with ligands 1a-e provided high enantioselectivities (up to 96%) in asymmetric allylic alkylation reactions. Display omitted •Sterically more demanding N-substituents distort the chelate to a larger extent along one single, conformational pathway.•The careful variation of the N-substituent allows a precise stereochemical fine tuning of the metal's coordination sphere.•The rationalization of the geometry allowed the development of a qualitative stereomodel for asymmetric induction.•Highly active and selective (ees up to 96%) Pd catalysts were obtained in allylation reactions.