过渡金属催化下若干碳氮、碳磷π键配位导向的碳氢键官能化反应

项目名称： 过渡金属催化下若干碳氮、碳磷π键配位导向的碳氢键官能化反应

项目编号： No.21272117

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： 孙培培

作者单位： 南京师范大学

项目金额： 80万元

中文摘要： 开发新的碳氢键活化方法以实现复杂化合物的合成是现代化学研究领域极富挑战性的课题之一，反应物中导向基团对反应的活性和选择性有关键性的作用。近年来，n型配位基团作为导向基团在选择性碳氢键官能化反应以及复杂有机化合物合成中备受关注，并已表现出巨大的应用价值。可以预期，π型配体在导向碳氢键官能化反应中应该同样具有很大的发展潜力。本项目拟研究过渡金属催化下碳―氮、碳―磷π键配位基团如氰基、磷叶立德等导向的碳氢键官能化反应。过渡金属催化剂可以是钯、钌、铑、铂等金属的化合物或配合物，被活化的碳氢键包括芳环上的sp2C―H键和烷基上的sp3C―H键，所导入的官能团包括芳基、烯基、烷氧基、三氟甲基、氨基、卤素等。通过对催化剂、溶剂、介质酸碱性、配体、氧化剂、反应温度、反应时间、反应气氛等反应条件的系统探究，获得实现这些反应的途径，由此建立若干合成多官能团化合物的新方法，并用于较复杂化合物的合成。

中文关键词： 过渡金属；催化；碳氢键官能团化；π-配体；自由基反应

英文摘要： The development of methods for the functionalization of relatively unreactive C-H bonds in order to discover fundamentally new routes to synthesize valuable organic products is one of the major challenges of modern chemistry. The directing group in starting material plays a key role in this transformation. Generally, it is considered that the Lewis basic groups with coordination properties involve n, π and ? types, in which n-type ligands have been widely used as directing groups in the high selective direct C-H bond functionalization reactions, while there are few reports of π-type ligands used for these purposes. In this research project, the transition metal-catalyzed C-H functionalization reactions directed by π-type coordinating groups, such as cyano and P-ylide groups will be studied. The compounds or complexes of the transition metals such as Pd, Ru, Rh and Pt will be used to catalyze the C-H functionalization reactions. The activations of sp2C―H bonds on aromatic rings and the sp3C―H bonds on alkyl groups will be studied. The introduced groups may be aromatic group, alkenyl group, alkoxyl group, trifluoromethyl group, amino group, halogen, atc. Through systematical studies to the various reaction parameters such as catalyst, solvent, ligand, acidity, oxidant, reaction temperature and reaction time, the o

英文关键词： transition metal；catalysis；C-H functionalization；π-ligand；radical reaction