Application of mixed phosphorus/sulfur ligands based on terpenoids in Pd-catalyzed asymmetric allylic substitution and Rh-catalyzed hydrogenation

A small library of easily prepared diamidophosphite-sulfides based on 1,3-thioether alcohols, primarily of terpenoid nature, was developed. Upon complexation with Pd( ii ) ions, these hemilabile ligands showed the ability to form both P , S -chelates and complexes with two ligands P -monodentately bonded to the metal. The structures of the ligands and their complexes were determined by 2D NMR spectroscopy and X-ray diffraction. The use of these stereoselectors provided up to 95% ee in the classic Pd-catalyzed asymmetric allylic substitution reactions of ( E )-1,3-diphenylallyl acetate with C- and N-nucleophiles and up to 80% ee in the Pd-mediated allylic alkylation of cinnamyl acetate with β-ketoesters. In addition, ee values of up to 90% with quantitative conversion were achieved in the Rh-catalyzed asymmetric hydrogenation of methyl esters of unsaturated acids. The effects of the structural parameters, reaction conditions and ligand-to-metal ratio on the catalytic results are discussed. Diamidophosphite-thioethers with terpenoid bridging moieties have been prepared and used in asymmetric transition-metal catalysis for the first time.