AI Article Synopsis
- A new library of diamidophosphite-sulfides, made from terpenoid 1,3-thioether alcohols, was created and shown to effectively complex with Pd(II) ions, forming various ligand bonding configurations.
- The study utilized 2D NMR spectroscopy and X-ray diffraction to determine the structures of the ligands and their metal complexes.
- The ligands achieved impressive enantioselectivity (ee) in several reactions, such as up to 95% ee in Pd-catalyzed asymmetric allylic substitutions and up to 90% ee in Rh-catalyzed asymmetric hydrogenation, with an analysis of how structural factors and reaction conditions influenced these results.
Article Abstract
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 ,-chelates and complexes with two ligands -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 ()-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.
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