Trans Effect of Different Coordinated Atoms of Planar Chiral Ferrocene Ligands with the Same Backbone in Palladium−Catalyzed Allylic Substitutions

A series of planar chiral P,S-, P,(C N)-, and S,(C N)-bidentate ferrocenyl ligands 4, 5, 8, and 9 with the same central and planar chiralities were prepared from the commercially available starting material N, N -dimethyl-( S )- α -ferrocenylethylamine. A Pd-catalyzed asymmetric allylic alkylation reaction was used as a model reaction to study the trans effect of the coordination atoms by these ligands. On the basis of the reaction results and the study of X-ray diffraction as well as 1 H and 13 C NMR spectra of the complexes ( 12 − 15 ), the sequence of the trans effect was established as C N > P > S, which was supported by molecular modeling at the PM3 level.