金属铜催化的惰性碳氢键活化反应的研究

As we all know, C-H bond is the most simple and common functional group among the organic compounds. The chemical synthesis based on C-H bond activation is the most economical,simple and efficient method, which can not only simplify the materials, shorten the process of reaction, but also make much more target products those were difficult to get by conventional methods. So the development of new method about C-H functionalization to synthesize more valuable C-C bond and C-X bond (X=halogen, oxygen, sulfur and nitrogen et al) is one of the most important challenges and goals in the modern organic synthesis. Relative to the Rhodium and Palladium, less people pay attention to the application of copper in this area. However, compared with the former two metals, the Copper is not only cheap, abundant, but also less toxical.Its use in this field will be very much in line with the development trend of modern green synthetic chemistry. This project is to design the novel method on the C-H bond activation for more efficient and economical way in this field, which is based on copper as the catalyst in the C-H functinalization.

C-H键是有机化合物中最简单、最常见的官能团，基于C-H键活化策略的化学合成可以简化原料、缩短反应流程，能够实现常规方法难以制备的目标产物，是最经济、最简洁、最高效的途径，因此通过C-H键的活化直接产生C-M键，进而通过转换和淬灭从而产生新的C-C、C-X(X=卤素,氧硫和氮等等)键是现代有机合成中最为重要的挑战和目标。相对于金属铑和钯,金属铜在这一领域的关注相对较少。而铜与前二者相比，不仅储量丰富， 廉价，而且毒性小，它在这一领域的使用将非常符合现代绿色合成化学的发展趋势。本项目就是围绕金属铜作为催化剂来设计新颖的碳氢键官能团化反应，为这一领域提供一条更为经济高效的途径。

虽然金属催化的C–H键活化得到了迅猛发展，但是目前这些反应主要集中在使用铱、铑和钯等贵金属；从经济性和可持续发展的角度出发，寻找更为廉价的金属作为催化剂将是这一领域未来的重要发展趋势。金属铜由于具有廉价、储量丰富，且毒性小易操作等特点，在发展催化C–H键活化方法学中具有广阔的前景。然而对于铜催化的C–H键活化的机理尚不明确，这主要是因为铜原子化学价态的多样性以及易发生单电子转移过程的缘故，导致其反应机理相对于钯化学更为复杂。申请人通过导向基团的合理设计和催化体系调控，在铜参与的系列C–H键活化和官能团化方面， 取得了阶段性的研究成果；具体分为C–C(sp, sp2, sp3)键和C–X（杂原子）键的构建；以及导向基配位能力-控制反应选择性。一共发表SCI论文13篇，其中1篇J. Am. Chem. Soc.，1篇Angew. Chem. Int. Ed. ，3篇Chem. Sci.等。