Novel alkane-diyl based heterobidentate P,N and S,N ligands with the general formula R1R2NCH(R3)(CH2)nCH(R4)Q (R1 = Me or iPr; R2 = H or Me; R3, R4 = H or Me; n = 0, 2; Q = PPh2 or SPh) have been prepared starting from cyclic sulfate esters or naturally occurring compounds with C1 symmetry. The length of the ligands’ backbone and the reaction conditions applied strongly affected the stereochemical outcome of the synthesis when using cyclic sulfates as starting materials. Palladium(II)-complexes of the new ligands were characterized by 1D and 2D NMR spectroscopy in solution and in several cases by X-ray crystallography in the solid phase. The structural versatility of the ligands enabled the straightforward comparison of the stereoselectivity of their coordination as a function of their tether length, backbone substitution pattern, donor sets and relative carbon atom configuration in their backbone. The catalytic features of the novel compounds were investigated in asymmetric allylic alkylation reactions where the tether length proved to be a crucial factor in determining enantioselectivity. Display omitted