Synthesis of Solid-state Metal Phosphate Catalysts Having Chiral Structure

为了探索不对称有机合成的手性固体催化剂，合成了具有金属离子和有机胺阳离子的环己基磷酸盐的各种结构材料。所有合成的晶体材料都进行了结构表征。脂肪胺的有机阳离子对结构的形成非常重要，因为与有机阳离子中和的单体环己基磷酸盐阴离子通过有机阳离子之间的氢键连接在一起，从而在结构中形成二维网络。当体系中存在金属阳离子时，金属阳离子起到连接环六磷酸根阴离子的作用，形成一条无限的金属阳离子链--环己磷酸盐，其正向变化又被有机阳离子所中和，从而形成三维网络。在芳香族氨基化合物中，由于两个相对位置的有机阳离子-环己基磷酸盐单元的苯环之间发生了pi-pi相互作用，所以大多数结晶材料都是层状结构。在此基础上，我们进一步尝试利用手性有机化合物或手性金属络合物来设计结构中具有手性环境的材料。

Various structural materials of cyclohexaphosphate with metal ions and cations of organic amines were synthesized with the intention of exploring chiral solid catalysts for asymmetric organic syntheses. All the synthesized crystal materials were characterized structurally. The organic cations of aliphatic amines are very important for forming structures because the monomeric cyclohexaphosphate anions neutralized with the organic cations were linked together through hydrogen bondings between the organic cations, thus forming two-dimensional network in the structures. When metal cations are present in the system, the metal cations play a role to connect cyclohexaphosphate anions, and then a infinite chain of metal cation-cyclohexaphosphate is formed, of which positive change is neutralized with again the organic cations which allows the formation of three-dimensional networks. In the case of aromatics amincs, most crystallized materials were layred structures because pi-pi interaction occurred between phenyl rings of two opposite positioned organic cation-cyclohexaphosphate unit. On the basis of the structural information of the cyclohexaphosphate compounds, we further tried to design materials having chiral circumstance in the structure using chiral organic compounds or chiral metal complexes.