金催化的 C-H 键选择性活化及 C-C 交叉偶联反应研究

项目名称： 金催化的 C-H 键选择性活化及 C-C 交叉偶联反应研究

项目编号： No.21202105

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 有机化学

项目作者： 宋飞杰

作者单位： 四川大学

项目金额： 25万元

中文摘要： 近年来，过渡金属催化的C-H官能化构建C-C键的方法成为有机化学领域的一大热点。该方法由于可以避免或减少传统的R-X/R-M偶联反应中原料的预活化过程，因而更加符合高效性及原子经济性原则。从文献来看，传统过渡金属如Pd、Rh、Ru等催化的C-H键活化构筑C-C键的方法普遍存在催化剂用量高、反应条件苛刻、底物普适性有限等不足。为解决这些科学问题，本申请拟利用Au独特的化学性质，开展多种类型的Csp2-H键尤其是Csp3-H键在Au催化下与有机金属试剂之间的交叉偶联反应（C-H/C-M型），甚至与不饱和化合物 C-H键之间的直接交叉脱氢偶联反应（C-H/C-H型），充分认识反应机理，并进一步发展出传统过渡金属催化难以实现的C-C键构筑的新反应、新方法，为特定功能分子的合成提供简洁、高效、原子经济的合成途径。课题的成功实施将拓展金催化化学的范围，为有机合成化学的发展做出贡献。

中文关键词： 金催化；C–H键活化；C–C偶联反应；温和的反应条件；机理研究

英文摘要： In recent years, the transition-metal-catalyzed C-H activation/C-C coupling reactions, which can avoid or eliminate the "preactivation" process of conventional R-X/R-M cross-coupling reactions, has attracted much attention and become one of the hot topics in organic chemistry owing to its high efficiency and atom economy. However, the traditional transition-metal (such as Pd, Rh, Ru etc.)-catalyzed C-C bond forming reactions from C-H activation are generally suffering from high catalyst loading, harsh reaction conditions and limited substrate scope. To solve these problems, this proposal intends to study gold-catalyzed coupling reactions of various Csp2-H or Csp3-H bonds with organometallic compounds (C-H/C-M mode), and even the direct dehydrogenative coupling reactions with unsaturated C-H bonds (C-H/C-H mode) by taking advantages of the unique properties of gold. Furthermore, novel C-C bond forming strategis, which are difficult to be achieved by other transition-metal-catalyzed reactions, will be disclosed with in-depth understanding of the reaction mechanisms. Highly efficient and atom-economic synthetic approaches for important functional molecules will be developed by the utilization of these protocols. The realization of this project will expand the scope of gold catalysis and make contributions to the de

英文关键词： gold catalysis；C–H activation；C–C cross-coupling；mild reaction conditions；mechanistic study