The Study On Carbon-carbon Coupling Reaction For Synthesis Of Drug Intermediates Catalyzed By Porous Organic Phenanthroline-based Polymers

The formation of C-C bond is an important part in organic chemistry,and the coupling reaction catalyzed by transition metal is a common means to construct C-C bond.however,as people pay more attention to green,efficient and highly selective reactions,more and more researches have been conducted on coupling reactions without transition metal catalysis.In recent years,many new catalytic systems have emerged,giving rise to a variety of reaction types,such as oxidative coupling,reduction coupling and direct activation of C-H bond（functional group）.Coupling reaction is mainly divided into C（sp²）-C（sp³）,C（sp³）-C（sp³）,C（sp²）-C（sp）,C（sp³）-C（sp）,C（sp²）-C（sp²）type coupling reaction.The first part of this study mainly focuses on the C（sp²）-C（sp²）type coupling reaction to generate biaromatic stent drug intermediates,and provides a new design idea of heterogeneous catalyst directly activated by C-H bond.The second part mainly studies the C（sp²）-C（sp）type coupling reaction to generate benzonitrile drug intermediates.Part I:A novel porous organic phenanthrolin-based polymer was designed and synthesized.The material has high surface area,abundant mesoporous and excellent chemical stability.As a heterogeneous catalyst,it shows excellent activity and recoverability in direct C-H bond activation（arylation）of aromatics catalyzed without transition metal.Under the single electron transfer mechanism,the catalytic activity of heterogeneous catalyst is enhanced due to the joint action of adsorption effect and electron-donating effect,and the activity of heterogeneous catalyst is higher than that of homogeneous catalyst.A novel transition metal-free heterogeneous catalyst for the direct activation of aromatic C-H bonds was provided,and a new mesoporous organic polymer was synthesized,which provided a new idea for the construction of mesoporous organic polymer catalytic materials.PartⅡ:Novel cross-linkers were developed after the preliminary exploration and synthesis,and a series of porous organic phenanthrolin-based polymers were synthesized.Moreover,they all possess high specific surface area,abundant mesoporous and excellent chemical stability.Subsequently,the coordination properties of Pd（OAc）₂ of these porous organic phenanthrolin-based polymers were investigated,and it was found that they have good stability while guaranteeing high specific surface area.In order to explore the stability,coordination performance and post-coordination catalytic performance of these polymer materials,The catalyst after this series of porous organic phenanthrolin-based polymer materials and Pd（OAc）₂ coordination were used for cyanidation of halogenated aromatics,it has good catalytic activity,stability and recovery performance for different substrates.