功能化MCM-41负载铜催化剂的设计、合成及其催化碳-碳键和碳-杂键形成反应研究

Copper-catalyzed carbon-carbon bond and carbon-heteroatom bond formation reactions have become one of powerful tools in modern organic synthesis. However, homogeneous copper salts/ligands catalysts cannot be recycled, and are difficult to remove from the product, practical applications of these reactions are limited. Based on the principles of organic synthesis methodology and green chemistry, in this project we intend to design and synthesize a series of novel MCM-41-supported copper complexes catalysts by simple synthetic procedures and characterize them. The novel MCM-41-supported copper complexes will be used as heterogeneous catalysts in a variety of copper-catalyzed carbon-carbon coupling and carbon-heteroatom coupling reactions, and in the synthesis of various kinds of nitrogen heterocycles compounds via one-pot cascade reaction. They will also be used to develop some new organic reactions. We expect that heterogeneous copper catalysts with high activity and excellent recyclability for some coupling reactions will be found by optimization of reaction conditions and investigation of the relationship between catalyst structures and catalytic activities. The use of highly efficient heterogeneous copper catalysts helps to reduce cost of the reaction, to minimize wastes derived from reaction workup, and to prevent product from contamination by copper. Our research work will provide a theoretical basis for the applications of copper-catalyzed coupling reactions in large-scale laboratory preparation or in industry production.

铜催化碳-碳键和碳-杂键形成反应已成为现代有机合成的重要工具之一。然而，均相铜盐/配体催化剂难以与产物分离和回收再用，且易污染产物，其实际应用受到限制。本项目以有机合成方法学和绿色化学基本原理为理论依据，通过模拟高活性的均相铜盐/配体催化剂结构，设计、合成系列新型MCM-41负载双齿氮铜、双齿氧铜、氮-氧混合双齿铜、硫-氧混合双齿铜、三齿氮铜等配合物催化剂，并对其结构进行表征。研究其在铜催化的各种碳－碳、碳－杂偶联反应及在经"一锅"串联反应合成各种含氮杂环化合物中的应用，并探索其拓展一些新有机反应的可能性。通过优化反应条件，研究催化剂结构与催化活性之间的关系，有望筛选出对某些偶联反应具有高活性和优异回收再用性能的负载铜催化剂。高活性负载铜催化剂的应用将有助于降低反应成本和减少废弃物排放，使产物不受铜污染，为铜催化重要有机反应能应用于实验室大规模制备及工业化应用奠定基础。

本项目通过模拟高活性的均相铜盐/配体催化剂结构，设计、合成了系列新型MCM-41负载双齿氮铜(I) (MCM-41-2N-CuX)、MCM-41负载席夫碱、吡啶双齿碘化亚铜(MCM-41-Sb,Py-CuI)、MCM-41负载联吡啶碘化亚铜(MCM-41-bpy-CuI)、MCM-41负载三齿氮碘化亚铜(MCM-41-3N-CuI)、MCM-41负载L-脯氨酸铜(I) (MCM-41-L-proline-CuX)和MCM-41负载三齿氧碘化亚铜(MCM-41-3OH-CuI)等配合物催化剂，并用氮气吸附与脱吸附、小角X-射线衍射、元素分析和等离子体发射光谱等对其结构进行了表征。继而研究了MCM-41负载双齿氮碘化亚铜配合物(MCM-41-2N-CuI)在催化吲哚的Ｎ-芳基化反应，芳基卤化物与硫代乙酰胺的交叉偶联反应，2-溴苯甲酰胺和β-酮酸酯的串联反应以及四氢异喹啉与醛、端炔的A3偶联反应中的应用；研究了MCM-41负载双齿氮氯化亚铜配合物(MCM-41-2N-CuCl)在催化芳基碘化物与硫氰酸钾于纯水中的交叉偶联反应，2-碘苯胺与二硫化碳、胺的三组分串联反应，端炔与硫酚的交叉偶联反应中的应用；研究了MCM-41负载三齿氮碘化亚铜配合物(MCM-41-3N-CuI)在2-卤苯甲酸与脒的串联反应中的应用；研究了MCM-41负载席夫碱、吡啶双齿碘化亚铜配合物(MCM-41-Sb,Py-CuI)在端炔与芳基卤化物的Sonogashira偶联反应中的应用；研究了MCM-41负载联吡啶碘化亚铜配合物(MCM-41-bpy-CuI)在有机硼酸与二芳基二硒醚的碳-硒偶联反应，初级苄醇或烯丙醇的空气氧化反应中的应用；研究了MCM-41负载L-脯氨酸铜(I)配合物(MCM-41-L-proline-CuX)在芳基硼酸与NCS或NBS的卤化反应及MCM-41负载三齿氧碘化亚铜配合物(MCM-41-3OH-CuI)在芳基碘化物与硫酚的交叉偶联反应中的应用。通过优化反应条件，研究负载配合物催化剂结构与催化活性之间的关系，已筛选出对某些偶联反应具有高活性和优异回收再用性能的负载铜催化剂。高活性负载铜催化剂的应用将有助于降低反应成本和减少废弃物排放，使产物不受铜污染，为铜催化重要有机反应能应用于实验室大规模制备及工业应用奠定基础。