A series
of structurally diverse diamidophosphite-sulfides were
synthesized from 1,2-thioether alcohols. With respect to Pd(II), these
hemilabile ligands showed the ability to form both P,S-chelates and complexes with two ligands connected
to the metal P-monodentately. The structures of the
ligands and complexes were confirmed by two-dimensional (2D) NMR spectroscopy
and single-crystal X-ray diffraction. These stereoselectors provided
up to 98% ee in the Pd-catalyzed asymmetric allylic
substitution of (E)-1,3-diphenylallyl acetate with
C- and N-nucleophiles and up to 78% ee in the Pd-mediated
allylic alkylation of cinnamyl acetate with β-ketoesters. Furthermore,
up to 71% ee was achieved in the rare reaction between
2-(diethoxyphosphoryl)-1-phenylallyl acetate and aniline. The effects
of the structural parameters, reaction conditions, and ligand-to-metal
ratio on the catalytic results are discussed. Due to the ability of
the ligands to form structurally different catalytic species, a pronounced
dependence of the asymmetric induction on the ligand-to-metal ratio
is shown.