Asymmetric Epoxidationandhydrophosphonylation Reaction Catalyzed By Rare-Earth Metal Silylamides [（Me₃Si）₂N]₃Re（μ-Cl）Li（THF）₃/Phenoxy-functionalized Chiral Prolinols

Ten phenoxy-functionalized chiral prolinolcompounds were designed and well prepared.Rare-earth metal amides REN(TMS)2]3(μ-Cl)Li(THF)3were treatedwith these ligands in situ and the application of the combinationon asymmetric epoxidation α,β-unsaturated ketones andenantioselective hydrophosphonylation of α,β-unsaturated amides were investigated.1. A series ofphenoxy-functionalized chiral prolinolcompounds with Afferent steric hinderance were designed and well prepared. They are: H2L1((2,4-di-tert-butyl-6-(((S)-2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phen ol)), H2L2((S)-2-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)-4,6-bis(2-Phenyl-propan-2-yl)phenol),H2L3(4-tert-butyl-2-(1-adamantanyl)-6-(((S)-2-(hydroxydiphenyl-methyl)pyrrolidin-1-yl)methyl)phenol), H2L4 ((S)-4-tert-butyl-2-((2-(hydroxydiphenyl-methyl)pyrrolidin-1-yl)methyl)-6-tritylphenol), H2Ls((S)-2-((2-(hydroxydiphenyl-methyl)pyrrolidin-1-yl)methyl)-4,6-dimethylphenol), H2L6((S)-2-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)-4-methylphenol), H2L7((S)-2,4-di-tert-butyl-6-((2-(hydroxymethyl)pyrrolidin-1-yl)methyl)phenol), H2L8((S)-2,4-di-tert-butyl-6-((2-(2-hydroxypropan-2-yl)pyrrolidin-1-yl)methyl)phenol), H2L9 ((S)-2-((2-(hydroxymethyl)pyrrolidin-1-yl)methyl)-4,6-bis(2-phenylpropan-2-yl)phenol), and H2L10((S)-2-((2-(3-hydroxypentan-3-yl)pyrrolidin-1-yl)methyl)-4,6-bis(2-phenyl-propan-2-yl)phenol).2.The application of the combination of complexes [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 with phenoxy-functionalized chiral prolinolson asymmetric epoxidationof α,β-unsaturated ketonesComplexes [(Me3Si)2N]3RE(μ-Cl)Li(THF)3(Ln= Yb, Y, La, Lu) with phenoxy- functionalizedchiral prolinolwere found to be highly efficient catalysts for asymmetric epoxidation of α,β-unsaturated ketones to give the corresponding chiral epoxides with high activity and goodenantioselectivity under mild conditions. It could be achieved 91-99% yield and 87-99% ee to different kinds of α,β-unsaturated ketones only with 4 mol% catalyst and 6 mol% chiral prolinol ligand. This catalyst systemhas the characteristics of simple, efficient, and wide applicability.3. Study on the mechanism of the combinantion of complexes [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 with phenoxy-functionalized chiral prolinolson asymmetric epoxidation of α,β-unsaturatedketonesReaction of phenoxy-functionalized chiral prolinol ligand H2L1 with the complex [(Me3Si)2N]3Yb(μ-Cl)Li(THF)3afforded a homodinuclear ytterbium complex [L1Yb(L1H)]. The structure of this complex was characterised and was tested as a catalyst in the asymmetric epoxidation of chalcone. The different kinds and ratios of alkali metals with [L1Yb(L1H)] on asymmetric epoxidation ofchalcone were studied as well.4. The application of complexes [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 with phenoxy-functionalized chiral prolinolson asymmetric epoxidation of α,β-unsaturated amidesComplexes [(Me3Si)2N]3RE(μ-Cl)Li(THF)3(Ln= Yb, Y, La, Lu, Sc) with phenoxy-functionalized chiral prolinol were found to be highly efficient catalysts for enantioselective hydrophosphonylation of α,β-unsaturated amides, which gave the corresponding chiral products with excellentyields and goodenantioselectivities in 1,4-dioxane.It is the first time that directly asymmetric hydrophosphonylation of α,β-unsaturated amideswas successfully catalyzed by rare earth metal catalysts.