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

• Published in: Organic & biomolecular chemistry Vol. 22; no. 31; pp. 6362 - 6369
• Main Authors: Gavrilov, Konstantin N., Chuchelkin, Ilya V., Gavrilov, Vladislav K., Firsin, Ilya D., Trunina, Valeria M., Shiryaev, Alexey A., Shkirdova, Alena O., Bermesheva, Evgeniya V., Tafeenko, Victor A., Chernyshev, Vladimir V., Zimarev, Vladislav S., Goulioukina, Nataliya S.
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 07.08.2024; Royal Society of Chemistry
• Subjects: Acetic acid; Alcohols; Alkylation; Asymmetry; Catalytic converters; Chelates; Chemical reactions; Chemistry; Chemistry, Organic; Esters; Hydrogenation; Ketoesters; Ligands; Magnetic resonance spectroscopy; NMR spectroscopy; Nucleophiles; Palladium; Physical Sciences; Rhodium; Science & Technology; Substitution reactions; Sulfur; Terpenes; X-ray diffraction; DIAMIDOPHOSPHITES; ALKYLATION; PERFORMANCE; ALLYLATION; COORDINATION; KETOESTERS; ENANTIOSELECTIVE CONSTRUCTION; DERIVATIVES; EFFICIENT; METAL-COMPLEXES
• ISSN: 1477-0520; 1477-0539; 1477-0539
• DOI: 10.1039/d4ob00840e

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 beta-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.