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Study On Pudovik Reaction Catalyzed By Lanthanide Silylamides

Posted on:2011-09-04Degree:MasterType:Thesis
Country:ChinaCandidate:Q M WuFull Text:PDF
GTID:2121360305484241Subject:Organic Chemistry
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The lanthanide amides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 catalyzed synthesis ofα-hydroxy phosphonates and the syntheses of chiral ligands derived from D-mannitol were studied in this thesis. The main contents of the thesis are as in the following.1. Lanthanide silylamides were found to be highly efficient catalysts for the synthesis ofα-hydroxy phosphonates via hydrophosphonylation of aromatic aldehydes, which is known as Pudovik reaction. The tetracoordinate lanthanide amides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 exhibited the catalytic activity which was superior to that of tricoordinate lanthanide amides Ln[N(SiMe3)2]3. The corresponding products involving various aromatic aldehydes and dialkyl phosphites could be obtained in excellent yields in the presence of 0.1 mol% [(Me3Si)2N]3La(μ-Cl)Li(THF)3 at room temperature within 5 min. The influence of lanthanide metal, alkali metal and halide on the catalytic activity was investigated and the mechanism for the process of high efficiency was proposed.2. D-mannitol is of many advantages as a precursor of chiral ligands. It is readily available, economical, and with C2-symmetry. A series of chiral ligands derived from D-mannitol, including 1,4-diols and oxazoline-functionalized compounds, were synthesized. The application of these ligands in lanthanum silylamide catalyzed Pudovik reaction was preliminarily explored.
Keywords/Search Tags:lanthanide silylamide, Pudovik reaction, α-hydroxy phosphonate, catalysis, synthesis, D-mannitol, chiral ligand, oxazoline
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