手性膦酸锆的原位合成与表征

不对称催化和对映体拆分是有机化学中最活跃的高技术领域，其中手性固体材料的设计与合成是极具挑战性的前沿课题之一.据Corey等研究的手性技术机理，手性固体一般应该具有空间允许、手性源为官能化的有机化合物和金属离子作为反应的活性中心等三大特征．然而，迄今同时具有上述特征的手性固体材料却很少．

In situ Synthesis and Characterization of Chiral Zirconium Phosphonates

The crystalline chiral zirconium phosphonates with α, γ-type structure, formulated as Zr(PO4)0.6(HPO4)0.1(O3PCH2NHC4H7COO-)0.55(O3PCH2NHC3H7COOH)0.55F0.55·H2O(mix-ZrPMP, α]D25=-36°) and Zr(PO4)0.6(HPO4)0.1(O3PCH2NHCH2SC2H3COO-)0.55(O3PCH2NHCH2S-C2H3COOH)0.55F0.55·2.0H2O(mix-ZrPMT, α]D25=-39°), were obtained in situ by reaction of N-phosphonomethyl-L-proline(H3PMP) and N-phosphonomethyl-1,3-thiazolidine-4-carboxylic acid(H3PMTA) with ZrOCl2·8H2O in the presence of HF at 90 ℃, respectively. The heterocycle thiazolidine was integrated onto metal-organic frameworks. Of mix-ZrPMP and mix-ZrPMT, the CO2H, CO2- and NH+ groups are remained in layered structures of mixed-type.