Hydrophosphoiiylation Catalyzed By Rare Earth Metal Amido Complexes And Synthesis Of Racemic Organolanthanide Complexes Controlled By The Intermolecular Coordination Of Heteroatom

This paper mainly concluded three parts: hydrophosphonylation ofaldehydes and ketones catalyzed by the methylene-linked pyrrolylrare-earth metal amides; hydrophosphonylation of α,β-unsaturatedcarbonyl compounds catalyzed by [（Me₃Si）₂N]₃Ln（μ-Cl）Li（THF）₃;controlled synthesis of the racemic organolanthanide complexes throughintermolecular coordination.1. Hydrophosphonylation of aldehydes and ketones catalyzed bythe methylene-linked pyrrolyl rare-earth metal amidesA series of rare earth metal amido complexes bearingmethylenelinked pyrrolyl-amido ligands were prepared throughsilylamine elimination reactions and displayed high catalytic activities inhydrophosphonylations of aldehydes and unactivated ketones. Study ofthe catalytic activities of the complexes showed that these rare earthmetal amido complexes were excellent catalysts forhydrophosphonylations of aldehydes and unactivated ketones. The systemworks well for a wide range of aldehydes and unactivated aliphatic,aromatic or heteroaromatic ketones, especially for substitutedbenzophenones, giving the corresponding-hydroxy diaryl phosphonatesin moderate to high yields. The catalytic system provides a direct, atomeconomic synthesis of α-hydroxy phosphonates. 2. Hydrophosphonylation of α,β-unsaturatedcarbonyl compoundscatalyzed by [（Me₃Si）₂N]₃Ln（μ-Cl）Li（THF）₃The rare earth metal amido complexes [（Me₃Si）₂N]₃Ln（μ-Cl）Li（THF）₃displayed high catalytic activities and high regioselectivity for theaddition of diethyl phosphite to α,β-unsaturatedcarbonyl compounds.Results showed that the substrates of α,β-unsaturatedcarbonylcompounds have effect on the regioselectivity of the addition reaction.Only1,4-addition occurred for addition of diethyl phosphite toα,β-unsaturatedamides, esters and chalcones. However,1,2-addition or1,4-addition to the ordinary α,β-unsaturatedaldehydes and ketones werefound.3. Synthesis of Racemic Organolanthanide Complexes Controlledby the Intermolecular Coordination of HeteroatomThe reactions of the Me2Si-bridged N,N-dimethylethylindenyl indenylligands with [（Me₃Si）₂N]₃Ln（μ-Cl）Li（THF）₃（Ln=Yb, Eu） have beenstudied. The lanthanide（II） complexes with Me2Si-bridgedN,N-dimethylethylindenyl ligands for Yb or Eu were obtained through thehomolysis of the Ln-N bonds. The lanthanide（III） chloride complex withMe2Si bridged N, N-dimethylethylindenyl ligand was synthesized throughthe metathesis reaction of lithium salt of the ligand with LnCl3（Ln=Sm）.Besides，we first synthesized the racemic organolanthanide complexesthrough intermolecular coordination with the activation of an adjacentC-H bond of the nitrogen atoms （Ln=Y, Sm）, and proposed a possiblemechanism.