Chiral β-Phosphino Sulfoxides as Chiral Ligands in Palladium-Catalyzed Asymmetric Allylic Nucleophilic Substitution Reactions.

The first attempt to use chiral β-phosphino sulfoxides as chiral ligands was successfully accomplished in a palladium-catalyzed asymmetric allylic alkylation and amination, providing extremely high enantioselectivity with chiral 2-(diphenyl-phosphino)phenyl 2-methoxy-1-naphthyl sulfoxide. The structure of the intermediary palladium complex chelated by the ligand was determined by the X-ray crystallographic analysis. The mechanism for the asymmetric induction is proposed on the basis of the stereochemical results obtained.