新型手性氮杂环卡宾多相金属催化剂的制备及性能研究

This project targets on solving the bottleneck problem of low reaction conversion and enantioselectivity in enantioselective heterogeneous catalysis. As metal-organic frameworks (MOFs) possess excellent ordered structure, high porosity and large surface area, we plan to develop a series of novel chiral heterogeneous catalysts derived from MOFs. The main strategy is about employing chiral N-heterocyclic carbene metal catalysts as organic linker to connect metal skeleton nodes. Based on both the theoretical and experimental studies of the combination of bifunctional chiral N-heterocyclic carbene ligands and metal centers, we hope to demonstrate their influence on the MOFs' structure, porosity, solubility and stability. Importantly, a series of significant asymmetric catalytic reactions will be tested by using these new chiral MOFs heterogeneous catalysts. In this investigation, we envision to reveal the kinetics of MOFs catalyst in asymmetric catalysis, the inherent relationship between the MOFs' chiral space and reaction stereoselectivity, and the theoretical model for reaction mechanism. Overall, we anticipate developing several efficient and practical MOFs catalysts for asymmetric catalysis, advancing the process of chiral heterogeneous catalysts materials, and enriching the research areas of supramolecular chemistry, materials chemistry and asymmetric catalysis chemistry.

本项目针对多相不对称催化反应转化率低、光学选择性差等瓶颈问题，考虑到金属-有机框架材料（MOFs）具有可设计易调控的有序结构、高孔隙率和大比表面积等优势，从有机功能基块和骨架节点相结合的设计出发，引入含附加配位点的手性金属-氮杂环卡宾催化剂作为有机基块连接金属节点定向合成手性MOFs催化剂，从理论和实验相结合的角度系统研究双功能手性氮杂环卡宾配体和金属中心对MOFs材料的结构、孔隙率、溶解性和稳定性的影响规律，进而，以一系列重要的不对称催化反应为探针，研究手性MOFs催化剂的不对称催化反应动力学，揭示反应活性、光学选择性与MOFs手性结构之间的内在关联，阐明此类手性催化剂在不对称催化反应中的作用机理，建立理论模型，总结其中规律，研制出高效实用的手性MOFs催化剂，推进手性多相催化材料的研究进程，并丰富配位化学、超分子化学、材料化学和不对称催化化学的研究内容。

本项目主要开展了新型过渡金属催化剂的制备及催化应用研究和金属-有机框架材料的制备及性质研究两方面的工作，并且取得了阶段性的研究成果。与此同时，我们还以过渡金属催化为主要手段，针对简单易得的联芳烃化合物，开展了碳氢键活化/去芳构化协同转化和动态动力学不对称转化的开创性研究工作。过去四年，项目主持人作为唯一通讯作者，已将部分成果以研究论文的形式公开发表于多个化学类权威期刊，包括J. Am. Chem. Soc. (2篇)，Angew. Chem. Int. Ed.(3篇)，Chem. Commun. (1篇)，Org. Lett. (2篇)，J. Org. Chem. (1篇) 。