Synthesis And Catalysis Of Immobilized Chiral Ligand On Organic Or Organic-inorganic Hybrid Zirconium Phosphate

Zirconium phosphate (α-Zr(HPO₄)₂-H₂O) is a kind of layered inorganic ion-exchangers, that is named as α-ZrP. In this thesis, the chiral amino compounds, chiral 2-aminoalconol and 1, 1'-Binaphthyl-2, 2'-diol ligands were immobilized on the zirconium phosphonate framework, and the asymmetric addition of diethylzinc to benzaldehyde had also studied. It was found that ZrCHPO₄)_x(O₃PRPO₃)_(2-x)/2[O₃PRPO₃=N, N-dimethylphosphonate- L-(-)-a -benzylamine, N, N-dimethylphosphonate-D-(+)-α-benzylamine and BINOL derivates] have no enantioselectivity for the addition of diethylzinc to benzaldehyde. Zr (RPO₃)₂ [RPO₃=(1R , 2S)-(-)-2-[N-(ethylphosphonic acid)]imino-l, 2-diphenylethanol] has good enantioselectivity with 51 % e.e. which only decreased at 6 % enantiomeric excess lower than those in homogeneous asymmetric catalysis for the addition of diethylzinc to benzaldehyde.we also designed a series of multiply chiral centre BINOL-based Phosphoramidites derivatives in this thesis. Their enantioselectivity for the asymmetric addition of diethylzinc to benzaldehyde had been detailed. It was found that the enantioselectivity is poor at ambient temperature, and the lower temperature and the addition of Ti(O¹Pr)₄ can improve the enantioselectivity.