手性超分子配位组装体的设计、合成及其在不对称催化反应中的应用

本研究项目将超分子化学、配位化学和不对称催化原理结合起来，设计、合成一些手性多齿配体和桥联砌块，然后与金属离子配位，形成均手性超分子配位组装体催化剂。这种组装体催化剂存在高密度催化活性单元，因此可以用作不对称催化，实现立体选择性和区域选择性的有机合成反应。通过调节手性配体结构单元和桥联单元的尺寸、体积、几何形状，可以控制手性组装体催化剂中微孔和孔道的大小。利用其微孔可调性以及孔洞受限性，可以同时实现催化活性和立体选择性控制。通过与均相催化时下的情况进行比较，提供超分子组装体催化不对称催化反应的特异性或优点。研究手性桥联配体的结构因素包括电子、立体和几何特性等因素对组装体催化剂的结构、催化活性以及非对映选择性的影响和控制，总结其规律性。研究组装体催化剂的催化活性规律，考察催化剂结构和稳定性的关系，为发展实用的手性超分子组装体催化不对称合成过程提供科学依据。

Based on the principles of supramolecular chemistry, coordination chemistry and asymmetric catalysis, some homochiral supramolecular coordination complexes (CSCCs) will be designed and synthesized through coordination of chiral multitopic organic ligands, coordinated linkers and metal ions. Due to the high density of catalytic active units, these frameworks can be acted as homochiral catalysts, and applied into asymmetric catalysis of stereo- and regioselective reactions. By adjusting the size, volume and geometry of the organic ligands as well as the coordination preference of the metal species, one can, in principle, control the size and the shape of the formed pores in the resulting frameworks. By the use of the pore matrices and chemical functionality of the cavities, both the catalytic activity and the selectivity can be tuned by through metal and ligand diversity. In comparison with the corresponding homogeneous catalysis, the distinctiveness and advantages of stereo- and regioselectivity can be demonstrated. It will be studied and summarized that the catalytic activity and the antipodal stereoselectivity of asymmetric reaction are influenced and controlled by the structural factors of homochiral bridging multitopic ligands, such as electronic property, steric hindrance and geometrical features of the frameworks. Additionally, In order to provide a scientific basis for further development of practically asymmetric catalysis of supramolecular coordination complexes, those will also be evaluated, including the regularity of catalytic reactivity, the relationship of the structure and the stability as well as the transformation of the assembly structures in the catalytic process.