水介质中芳香碳-杂原子偶联反应的可循环铜催化体系的研制及催化性能研究

In the field of organic synthesis, the discovery of efficient and new catalytic system is an important aspect to promote the methodological research of organical reactions. Green chemistry requires avoiding chemical Pollutions from the original source，including the use of non-toxic and safety raw materials and catalysts, avoiding or decreasing the use of organic solvents. Obviously， the recyclable catalytic system and environmentally friendly water Play key roles in realizing green chemistry. In this project, stable and recyclable ligands which be efficient in copper-catalized aromatic carbon-heteroatoms coupling reactions in water will be designed and synthesized. In addition, preparation and characterization of supported catalyst on modified inorganic or organic polymeric materials will be reserched. Some kinds of active ligands which have been applied in aromatic carbon-heteroatom coupling reactions in water will be immobilized on supporters through participating of different linkers. Then the inorganic or organic polymeric materials supported copper-catalysts are designed and synthesized through coordinating reactions between supported functional ligands with copper sources by impregnation or coordination methods. The catalytic activity of the synthesized supported catalysts will be investigated based on the coupling reactions between aryl halids with amines, phenols and thiophenols. And the ultimate goal is to find the efficient and recyclable copper catalytic system, and to reduce the water pollution of the organical reactions in water. This project is in accord with the atomic economic and environment-friendly principles, and it will realize the green chemistry of aromatic carbon - heteroatom coupling reactions in deed.

有机合成中高效的新型催化体系的发现是促进有机反应方法学研究发展的重要方面。而水相体系的绿色性和可循环催化体系的使用是发展绿色有机合成反应方法的有效途径。本项目拟通过设计合成出在所需反应条件下稳定的可循环使用的铜催化剂的高效配体化合物；或采用改性的无机载体或有机高分子载体进行催化体系的固载化研究，通过不同连接基的引入，将具有水相芳香碳-杂原子偶联反应催化活性的配体化合物接枝到改性后的无机载体或有机高分子载体上，再采用浸渍法或络合法引入金属铜，制备得到负载型铜催化剂，并用于水相体系中芳香碳-杂原子的偶联反应。课题研究的最终目标在于设计并合成出水相体系中可循环使用的高效的铜催化体系，减少水相有机合成反应中可能造成的水资源的污染，真正意义上的实现芳香碳-杂原子偶联反应的绿色性和原子经济性。

有机合成中高效的新型催化体系的发现是促进有机反应方法学研究发展的重要方面。水相体系的绿色性和可循环催化体系的使用是发展绿色有机合成反应方法的有效途径之一。此外，以清洁、安全的电子作为氧化还原试剂的电有机合成反应方法同样具有操作安全、环境污染小的优势，也是今后发展“绿色化学合成工业”的重要组成部分。通过该项目的研究，分别建立了一种均相水相可循环催化体系和两种高分子负载的非均相水相可循环催化体系，高效的促进了水相铜催化的芳香C-N偶联反应；建立了一种简单的、环境友好的水相体系中铜催化的domino反应合成4H-苯并吡喃衍生物的方法；发展了一种苝四甲酰二亚胺促进的间接电催化的芳香卤代物与吡咯及其衍生物的C-C偶联反应方法。该项目研究成果为安全且环境友好的有机反应方法学的发展做出了贡献，为芳香胺、4H-色烯及2-芳基吡咯类重要芳香烃类化合物的绿色工业化生产提供了可能。