应用于直接C-H键卤化的双核Pd配合物催化剂设计、合成及催化活性研究

项目名称： 应用于直接C-H键卤化的双核Pd配合物催化剂设计、合成及催化活性研究

项目编号： No.21502120

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 叶文静

作者单位： 沈阳药科大学

项目金额： 21万元

中文摘要： 模仿生物体金属酶的双核过渡金属催化剂由于双核的协同活化作用，相对单金属催化可以更高效地促进反应的进行，甚至实现一些其无法完成的化学过程。过渡金属催化直接C-H键官能化是当前有机合成最热点的课题之一，利用协同效应这一特征开发高活性高选择性的双核过渡金属催化剂来成功实现直接C-H键官能化，以使之高效的应用于范围更广泛的底物，从能源、经济及环境的角度考虑，都具有重大价值与意义。申请课题首次以直接C-H键卤化为模型反应，拟设计合成新型的以萘啶、联吡啶、菲罗啉及哒嗪等为桥联单元的N4配位双核Pd配合物催化剂，由于结构中五元及六元双金属Pd环的形成便利了反应过程中双金属中心的协同活化，催化效率将得到极大提高，解决当前直接C-H键卤化反应中存在的催化剂用量大、催化活性低等问题。通过对不同结构催化剂活性进行比较及反应机理研究，揭示双核催化剂的反应机制、协同活化原理及构建高效C-H键官能化催化剂的规律。

中文关键词： 双核金属配合物；含氮多齿配体；Pd催化；卤化；碳氢键官能化

英文摘要： On account of the synergistic activation between the binuclear metal centers, binuclear transition metal catalysts which imitate the stucture of biological metal enzyme can be more efficiently promote many chemical processes, and even achieve a number of new reactions that could not work through a single metal catalyst. Transition metal-catalyzed direct C-H bond functionalization is currently one of the most popular approaches in modern organic synthesis. Through developing high active and selective binuclear transition metal catalysts, cooperation between two metal centers could more successfully promote the direct C-H bond functionalization. Excellent catalytic system of direct C-H bond functionalization would have wider application and benefit energy, economic and environmental. The present item contemplate designing and synthesizing the first naphthyridine-, bipyridine-, phenanthroline-, and pyridazine-based N4-binuclear Pd complex catalysts applied in direct C-H bond halogenation, which may exist excellent catalytic activity due to the structure of the five- or six-membered Pd-ring facilitating synergy between the two metal centers, then to solve the problem about the large catalyst amount and low reactive activity in current direct C-H bond halogenation systems. Constituting the relationship between the structure character and the catalytic activity and investigating the mechanism, can help us explore the rule of binuclear catalyst synergy and building highly efficient catalysts for direct C-H bond functionalization.

英文关键词： Binulear complexes;Multidentate N-containing ligands ;Pd catalysis;Halogenation;C-H bond functionalization