Studies On The Formation Of Carbon-Heteroatom Bond Via Transition-Metal-Catalyzed C-H Functionalization

Transition-metal-catalyzed carbon-hydrogen bond to construct carbon-heteroatoms bond is a powerful strategy for the synthesis of various organic compounds. Due to the reaction is a simple, convenient, atom economy and environment-friendly method, it has made rapid progress in recent years. Although there have been developed various method which catalyzed carbon-hydrogen bond to construct carbon-heteroatoms bond, the formation of carbon-sulfur and carbon-phosphorus bond via transition-metal-catalyzed carbon-hydrogen functionalization in the heterocyclic compounds are not univesal. The paper describes these two types of carbon-heteroatoms bond formation via transition-metal-catalyzed carbon-hydrogen functionalization.This thesis includes the following three parts:Firstly, The development and application of the formation of carbon-heteroatoms bond via transition-metal-catalyzed arbon-hydrogen functionalization were summarized in detail. The main focus on the construction of carbon-nitrogen, carbon-oxygen, carbon-phosphorus and carbon-sulfur bond via transition-metal-catalyzed carbon-hydrogen functionalization. The reactions are classified by the types of carbon-heteroatoms bond, and introduced systematically.Secondly, We descried a novel copper-catalyzed thiolation of azoles in detail. This reaction creates an opportunity to construct various sulfur-containing heterocyclic compound. Both aryl thiols and aliphatic thiols are used as coupling partners, and furnished the thiolation products in moderate to good yields. The reaction is compatible with a wide range of heterocycles including oxazole, thiazole, imidazole and oxadiazole. Meanwhile, the reaction mechanism has been done preliminary.Thirdly, We presented in detail a highly efficient carbon-phosphine bond construction via cuprous chloride catalyzed C-H functionalization process, which is suitable for the synthesis of various3-phosphoindoles. Only H2as the byproduct was released in this reaction. Meanwhile, we studied on the reaction mechanism in detailed, including kinetic isotope effect experimental, radical capture experiments, hydrogen detection experiments and intermediates validation experiments. Preliminary mechanistic studies indicate that the reaction might involve a addition-elimination process.