Sets of hetero- and homoannularly bridged ferrocenyl aminophosphine and diphosphine ligands were investigated in palladium-catalysed allylic alkylation and amination reactions ([1-PPh2-2,1'-(alpha-R-CH(CH2)(2))-ferrocene]: (R-c,R-p)-1: R=N(CH3)(2); (R-c,R-p)-4: R=PPh2; (R-c,R-p)-5: R=PCy2; ([1-PPh2-2,3-(alpha-R-CH(CH2)(3))-ferrocene]: (R-c,R-p)-2: R=N(CH3)(2); (S-c,R-p)-3: R=N(CH3)(2); (S-c,R-p)-6: R=PPh2; (S-c,R-p)-7: R=PCy2). Diphenylprop-2-en-1-yl acetate and pent-3-en-2-yl acetate were used as the substrates and dimethyl malonate or benzylamine as the nucleophiles. Catalytic data were analysed and compared to those of PPFA (8) and Josiphos-type (9, 10) ligands ([1-PPh2-2-(alpha-R-CHCH3)-ferrocene]: (S-c,R-p)-8: R = N(CH3)(2); (S-c,R-p)-9: R = PPh2; (S-c,R-p)-10: R = PCy2). Correlations between changes in enantioselectivity or absolute configuration of product and changes in ligand backbones or functional groups were assessed. Cationic palladium(II) diphenylallyl complexes of ligands 1, 4, 5 and 7 were isolated and their conformational behaviour in solution was analysed both as the isolated complexes and under catalytic conditions. The molecular structure of complex 7C (endo syn/syn form) was determined by X-ray diffraction. (c) 2006 Elsevier B.V. All rights reserved.