金属-手性吡啶@MOF负载型催化剂的合成及其在不对称催化反应中的应用

Synthesis the chiral catalysts of high efficiency, high performance, easy separation, is a focus of the current study. Metal - organic frameworks (MOFs), have some unique properties, such as insolubility, large specific surface area, high porosity, adjustability of structure and function, applying in many fields. This project drawing up the unique characteristics of MOFs and the enantiotropy property of metal - chiral ligands, develops a synthesis simple and performance fine method of chiral support catalysts,. Through step by step method, we will have link the dual-functional chiral pyridine ligands in the MOFs system through covalent bonds, further coordinating to the metallic ions, forming a new kind of metal - chiral pyridine@MOF support catalysts, applying in the asymmetrical 1,4- addition reaction system of arylboric acids and α, β-unsaturated ketones. The best matchable catalytic system would be founded, by adjusting the crystalline form and size of MOFs, rational design the structure and functional groups of chiral ligands, exploring the best reaction system and conditions. The catalytic mechanism would be proposed combining the DFT theoretical study.

合成高效、高性能、易分离的手性催化剂是目前研究的一个热点问题。金属-有机框架材料(MOFs)具有难溶、大比表面积、高孔隙率、结构及功能的可调等特性而被广泛应用。本项目拟将MOFs特性与金属-手性配体的光学活性相结合，建立一种合成简便、性能优良的新型手性负载型催化剂的合成方法。通过分步合成法，将具有双功能基的手性吡啶类配体通过共价键连接于MOFs体系，进一步与金属离子配位，合成新型的金属-手性吡啶@MOF负载型催化剂，并应用于芳基硼酸与α,β-不饱和酮的不对称1,4-加成反应。通过调控MOFs的晶形和晶粒大小，设计手性吡啶类配体的结构和功能基团，摸索最佳的反应体系和条件，达到催化性能的最优化。结合DFT理论计算，探索催化反应机理。

金属-有机框架材料(MOFs)具有难溶、大比表面积、高孔隙率、结构及功能的可调等特性而被广泛应用。本项目利用MOFs特性与轴手性联吡啶配体的光学活性，通过金属离子交换、酰胺缩合等后修饰合成，建立了合成简便、性能优良的新型手性MOF催化剂和MOF负载型催化剂的合成方法，筛选出最优条件，研究了催化剂在芳基硼酸与α,β-不饱和酮的不对称1,4-加成反应中的催化性能，为新型手性催化剂的研发提供科学依据。