Asymmetric Hydrophosphonylation of α,β-Unsaturated Ketones Catalyzed by Rare-Earth Metal Complexes Bearing Trost Ligands

Chiral dinuclear rare-earth metal complexes RE2L2n (n = 1, RE = Y(1), Eu(2), Nd(3), La(4), Gd(5); n = 2, RE = Eu(6), Gd(7)) stabilized by the corresponding Trost ligands H3L1 or H3L2 (H3L1 = (S,S)-2,6-bis[2-(hydroxydiphenylmethyl)pyrrolidin-1-ylmethyl]-4-methylphenol, H3L2 = (S,S)-2,6-bis[2-(hydroxydiphenylmethyl)pyrrolidin-1-ylmethyl]-4-chlorophenol) were prepared and three unknown complexes 5-7 were characterized by X-ray diffraction analysis. The chiral rare-earth metal complexes 1-7 displayed high reactivity in the asymmetric hydrophosphonylation of alpha,beta-unsaturated ketones, and 5 mol % of complex 7 together with 10 mol % of chiral diamine (1S,2S)-1,2-cyclohexanediamine were proved to be the optimal catalyst combination. Various hydrophosphonylation products with excellent yields and high to excellent enantiomeric excess (ee) values were obtained in toluene (up to 99% yield, >99% ee).

Automated summary

Chiral dinuclear rare-earth metal complexes were synthesized and three unknown complexes were characterized. These chiral complexes showed high reactivity in the asymmetric hydrophosphonylation reaction, with complex 7 and chiral diamine proving to be the optimal catalyst combination. The reaction yielded hydrophosphonylation products with high yields and excellent enantiomeric excess values.