Study On The Hydrophosphonylation Reactions Of Aldehydes And Ketones Catalyzed By Lanthanide Anilido Complexes And Organic Alkalides

In this thesis, some lanthanide anilido complexes supported by2,6-diisopropylanilido ligand were synthesized and well characterized, and their catalytic activity for the hydrophosphonylation reaction was explored. In addition, the hydrophosphonylation reaction of aldehydes and unactivated ketones catalyzed by organic alkalides was also developed.1. Synthesis, characterization and catalytic property of lanthanide anilido complexesLanthanide anilido complexes stabilized by2,6-diisopropylanilido group were synthesized and well characterized, and their catalytic activity for the hydrophosphonylation reaction of aldehydes and unactivated ketones was explored. Reaction of anhydrous LnCl3with5equivalent of LiNHPh-Pri2-2,6in THF generated the heterobimetallic lanthanide-lithium anilido complexes (2,6-’Pr2PhNH)5LnLi2(THF)2[Ln=Sm (1), Nd (2), Y(3)] in good isolated yields. Reaction of anhydrous YCl3with3equivalent of NaNHPh-Pri2-2,6in THF generated the homoleptic lanthanide anilido complexes(2,6-’Pr2PhNH)3Y (4). It was found that these simple lanthanide anilido complexes are highly efficient catalysts for the hydrophosphonylation reactions of various aldehydes and unactivated ketones to generate a-hydroxy phosphonates in good to excellent yields (up to99%) within a short time (5min for aldehydes,20min for ketones). It was found that the presence of lithium ion is benefit to the reactions. The mechanism of hydrophosphonylation reactions catalyzed by these lanthanide complexes was proposed via1H NMR monitoring reaction.2. Organic alkalides as highly efficient catalysts for the hydrophosphonylation of aldehydes and unactivated ketones.It was found that organic alkalides, such as2,6-iPr2PhNHLi, LHMDS, LDA, n-BuLi, were highly efficient catalysts for the hydrophosphonylation reactions of aldehydes and unactivated ketones for the first time. The amount of the organic alkalides and reaction temperature play a key role on the reactions. For the hydrophosphonylation reactions of ketones, the yield of a-hydroxy phosphonates decreased as the increase of the amount of organic alkalides. Using0.1mol%n-BuLi as the catalyst, extremely high yields of the α-hydroxy phosphonates can be reached in a very short time (5min) under solvent-free condition.