过渡金属催化的含硫基团导向的C-H键活化反应研究

项目名称： 过渡金属催化的含硫基团导向的C-H键活化反应研究

项目编号： No.21272205

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 张玉红

作者单位： 浙江大学

项目金额： 80万元

中文摘要： 过渡金属催化的碳氢键活化反应已经成为由碳氢键直接构筑碳碳键和碳杂键的有力工具，显示出了巨大的绿色合成研究价值，是当前有机合成的重要研究领域。其中导向碳氢键活化的反应显示出了良好的反应活性和选择性，成为了这一领域的研究热点。含硫化合物是一个重要的化学工业品，被广泛应用于药物活性分子和功能材料的合成中。目前，有关N或O导向的碳氢键活化反应已经被深入研究，但有关硫导向的碳氢键活化反应还未见报道。最近，我们小组在这方面取得了一些进展。本项目拟开展过渡金属催化的硫导向C-H键活化反应研究，采用不同过渡金属如Cu、 Pd、Ru、Rh、Ni、Fe等，探索研究各种过渡金属催化剂和配体等对硫导向碳氢键活化反应的活性和选择性，深入研究过渡金属催化的硫导向碳氢键活化反应的反应途径、反应条件和反应机理，总结其反应特点和规律，从而发展和发现过渡金属催化的构筑含硫化合物的绿色合成新方法。

中文关键词： 过渡金属；碳氢键活化；含硫化合物；偶联反应；催化反应

英文摘要： Transition metal-catalyzed C-C and C-X bond formation via C-H activation has emerged as an effective and powerful tool in organic synthesis. In these transformations, the regioselectivity can be controlled through the use of directing groups (DG) that commonly bear a lone pair of electrons. A variety of directing groups containing nitrogen and oxygen atoms have proved to be efficient in the C-H bond activations. Sulfur has received much attention by the chemists of organic synthesis, coordination chemistry, biomaterials and functionl materials. However, there is extremely rare example for utilizing sulfur as chelation groups in C-H activation, possiblely due to its strong coordination ability. We have engaged in the studies of transition metal-catalyzed C-H activation reactions, and we found recently that thioether could be used as the only directing group for the Pd-catalyzed olefination of arenes. In this project, we will study reaction mechanism of the C-H activation reactions assisted by sulfur as DG and transition metal (Cu, Pd, Ru, Rh, Ni, Fe) as catalysts. We will examine the effect of catalysts and ligands to obtain the optimal reaction conditions, therefore establishing the sulfur directed C-H functionalizations. The results of this project may lead to the creation of green and economical synthetic met

英文关键词： transition metal；C-H bond activation；sulfur compound；coupling reaction；catalytic reaction