MOF-Pd催化水介质中芳基重氮盐参与的C-C偶联反应研究

Coupling reactions are the most important methods for the selective construction of the carbon-carbon bonds. However, many of these transformations were conducted in harmful organic solvents. As a result, the developing of some environmental benign coupling processes is becoming a very urgent project for chemists. Arenediazonium salts heve been utilized as reactive aryhlide and triflates surrogates in pd-catalyzed cross-coupling reactions for C-C bond formation. The intrinsic electrophilicity of daizonium salts comes from N2 being a superb leaving group, which allows the use of mild reaction conditions, and sometimes without an additional ligand and/or base. In this project, we try to developed novel green reaction system for C-C coupling reactions, mainly focused on two green modified protocols for the coupling reactions based on water solvent and MOF-Pd catalyst. We try to design efficient and convenient MOF-Pd catalyzed coupling reactions for C-C bond formation in aqueous medium. Meanwhile, the key issue of the “on water” reaction will be further investigated through the probe of the reaction mechanism. We are aimed to develop novel green reaction system of arenediazonium salts as substrates in aqueous media for C-C coupling reactions and accumulate experience of the “water” reaction by the implement of this project.

偶联反应是有机合成中构建C-C键的重要方法，对其绿色化和实用化研究是当今化学工作者面临的重要课题。目前，有关偶联反应构建C-C键的研究主要集中在钯催化和有机溶剂的基础上，在水介质中的绿色化反应研究相对较少。本项目主要围绕水相溶剂和MOF-Pd催化剂两方面对作为卤代芳烃和三氟甲磺酸芳基酯等亲电试剂的替代物芳基重氮盐参与的C-C偶联反应的绿色化进行研究，并力图将两方面相结合，优化反应条件，为C-C偶联合成提供一条简便、快捷、切实可行的绿色反应途径。另外，本项目还拟对相应反应的催化机理做初步的探讨。通过本项目的实施，可以进一步拓展绿色溶剂水介质反应的研究范围，并为更深入理解水相有机反应的本质及其应用积累经验。

偶联反应是有机合成中构建C-C键的重要方法，对其绿色化和实用化研究是当今化学工作者面临的重要课题。金属-有机骨架（metal-organic frameworks, MOFs）材料是由金属离子和有机配体通过自组装而成的具有多孔结构的特殊晶体材料。本项目致力于开发具有可重复利用的催化性能的MOFs材料用于C-C新键的构建。设计并合成了配位型Pd-MOF和负载型Pd@MOF两大类催化剂，并成功催化于醇溶剂中的Suzuki和Heck偶联反应。拓展了MOF材料的催化应用领域。该项目中实施的以芳基重氮盐为底物在醇溶剂中C-C键的构建方法，为过渡金属Pd催化C-C键的形成提供一条简便、快捷、切实可行的绿色反应途径。为构建更多的结构新颖的新材料、新药物实体分子提供了绿色环保的新路线。