过渡金属催化下有机硅试剂参与的偶联新反应研究

Organosilicon reagents have shown many unique advantages in organic synthesis, including low price, high stability, environmental benignity and easy operation. The application of organosilicon reagents in organic synthesis will greatly promote the vigorous development of organic chemistry. In this project, we focus on the development of high efficient strategies to expand the application scope of organosilicon reagents in organic synthesis. The three main studies in this project are: 1) Adopting the strategy of aryl radical coupling, we will develop a novel and efficient method to synthesize arylsilanes by using aryl halides and aryl amine as the starting materials, which are cheap, abundant and commercially available. 2) Studies of trans-metal catalyzed cross-coupling reactions of organosilicon reagents and functional transformations of arylsilanes will be carried out. Thereby, a series of methodologies will be established to construct various chemical bonds including C-C, C-O, C-S, C-N, C-F, C-CF3, and C-CN, et al. 3) In metal catalytic reaction, the key intermediates in the process of reaction are organometallic complexes. In order to investigate the reaction mechanism, single crystals of these key intermediates will be tried to prepared and their structures will be confirmed by the X-ray crystallographic analysis.

有机硅化合物是一种廉价、高稳定性、环境友好和容易操作的有机金属试剂，将有机硅化合物应用于有机合成反应将会促进有机化学的蓬勃发展。本项目旨在通过高效的研究策略来拓展有机硅试剂在有机合成中的应用范畴。主要研究内容为：1）通过芳基自由基偶联策略，以底物范围广、廉价易得的卤代芳烃或芳基胺化合物为原料, 发展一种高效合成芳基硅试剂的新方法；2）研究一系列过渡金属催化下有机硅试剂与各种底物发生交叉偶联反应和芳基硅官能团转化反应，从而发展系列构筑C-C键, C-O键、C-S键、C-N键、C-F键、C-CF3键和C-CN键等的方法；3)反应过程中的关键中间体是金属络合物，我们拟合成系列含有配体的金属络合物并培养单晶，通过X-ray单晶衍射仪进行结构测定来进行机理研究。

作为一类重要的有机金属试剂，有机硅试剂具有高稳定性、易操作、环境友好等优点。自20世纪80年代以来，有机硅试剂在过渡金属催化的交叉偶联反应构筑C-C键(Hiyama偶联反应)得到了广泛应用。本项目主要以活性较高的三烷氧基芳基硅烷为芳基化试剂，研究了系列过渡金属催化的交叉偶联反应，从而拓展有机硅试剂在有机合成中的应用范畴。主要内容包括：1）以三烷氧基芳基硅烷为芳基化试剂，发展了过渡金属Co、Rh催化下吲哚（啉）、非环烯酰胺和苯甲亚胺酸乙酯的C-H芳基化反应；2）以三烷氧基芳基硅烷为芳基源，实现了廉价金属铜促进下Ar-P和铜催化下Ar-N键的构筑；3）通过氘代实验、KIE研究、自由基淬灭和分子间竞争实验等手段对反应机理进行了初步探究。