新型金属-有机骨架非均相催化剂构筑及其在[2+2+2]环加成反应的催化性能研究

Metal-organic frameworks (MOFs) can be used as heterogeneous catalysts with high efficiency, high selectivity and recovery. However, their limited species resulted in relatively narrow applications. In this project, we will directionally prepare a variety of metal-organic framework compounds with specific pore structures based on the design of several types of peculiar multidentate bridging ligands as the molecular tectons, which were embedded specific groups such as N,N, N,P, carbene, alkene/phosphine. Subsequently, metalation of the constructed MOFs with metal salts fabricated the desired novel heterogeneous catalysts, which were also designed via postsynthetic strategy after derivation of amine group in the MOFs-NH2 with good stability. Furthermore, the catalytic properties of the target materials in the [2+2+2] cycloaddition of oxime-alkyne and mono-alkynes were intensively investigated. The intrinsic relationship between the structure of MOFs and catalytic properties, and the influence of pore structure, specific group, metal active center on the catalytic performance were clarified and summarized. On this basis, the synergistic effect originated from the interplay of two or more physicochemical properties of the target materials will be further explored. Besides, the reaction mechanism can be achieved through the study of the interaction model between MOFs catalyst and reactant molecule. As a consequence, the progress and breakthrough obtained from the relevant investigation towards this project will develop a series of MOFs-based catalysts with high-efficient catalytic performance, laying the foundation for the further realization of challenging organic reactions.

金属-有机骨架化合物（MOFs）可以作为高效、高选择性、可回收的非均相催化剂，但其种类有限，适用的反应范围窄。本项目通过设计几类内嵌N,N、N,P、卡宾、烯膦等特定基团的多齿桥联配体，与金属离子定向自组装获得具有特定孔道结构的MOFs材料，再经过适当的金属化操作制备新型MOFs非均相催化剂，并将对稳定性好的MOFs-NH2中的胺基进行衍生化，采用后合成策略引入新的催化活性位点。重点进行目标材料在肟-炔与单炔的[2+2+2]环加成反应中的催化性能研究，阐明其结构与催化性能之间的内在关系，揭示孔道结构、特定基团等因素对催化性能的影响，探索目标材料两种或两种以上理化性能相互影响下的协同催化效应，通过研究MOFs催化剂与客体反应物分子的作用模式，揭示反应的本质规律。本项目的成功实施有望发展出多种高催化活性的MOFs催化剂，为实现具有挑战性的有机反应奠定基础。

金属-有机骨架化合物（MOFs）作为高效、高选择性、可回收的非均相催化剂，一直是材料合成与催化领域的研究热点。其中，MOFs在催化硅氰化反应、克脑文盖儿反应、偶联反应中应用广泛，但是对于C-H键活化、环加成反应等还鲜见报道。本项目合成出具有特定孔道结构的Co-MOF-1和Cu-537-MOF，先后实现了Co-MOF-1催化二炔与单炔的[2+2+2]环加成反应，产率高达95%，获得了孔道的尺寸效应以及催化剂对炔的吸附能力影响反应选择性和产率的初步结论；Cu-537-MOF催化N-苯基苄脒的分子内C-H键活化反应，产率高达96%，螺旋桨型铜催化剂中{Cu2(O2C)4}二级构筑单元(SBU)和TPPB2-中的四个羧酸配体是催化反应的关键。受脒C-H键活化反应的启发，通过优化不同的催化体系，先后完成了Cp*Rh(III)/Ag2CO3催化脒与二炔的C-H活化/[5+1]环化/5-环外环化反应，高收率地构建喹唑啉产物；Cp*Rh(III)/Mn(OAc)3•2H2O催化脒与分子间炔的多步C-H键活化串联反应，构建出喹唑啉基多环芳基化合物；Cp*Rh(III)催化脒与分子间炔的双重C-H键活化反应，制备苯并咪唑衍生物；Pd(OAc)2与分子间炔C-H键活化串联反应构建脒基八元环钯化合物。这些方法的发展为含氮杂环的构建提供了高效的合成方法。作为项目扩展，我们实现了钯催化邻苯二甲酰亚胺与苯炔以及铑催化邻苯二甲酰亚胺与分子间炔的脱羰基环化串联反应，为喹啉酮类化合物的构建提供了高效可行的方法。这些项目内容的成功实施不仅有望激励发展出多种高催化活性的MOFs催化剂，还能丰富C-H键活化领域的理论体系，为新反应的设计和开发提供了有价值的指导经验。