Studies On Transition-Metal-Promoted New Type Carbon-Phosphorus Bond Formation

Compared with traditional methods of carbon-phosphorus bond formation, the method of transition-metal involved carbon-phosphorus bond fomation to synthesis organophosphorus compounds is a more simple and efficient strategy. Since the strategy is an atom economy and environment-friendly method, many methods to construct carbon-phosphours bond by using different transition-metals have been proposed from the eighties of last century. These methods are not only convenient and practical, but also provide a variety of ways for the synthesis of organophosphorus compounds. In which, the method to form carbon-phosphorus bond via direct carbon-hydrogen bond functionalization is the most efficient. The approach is also our main tactics to synthesis organophosphorus compounds. The paper describes three methods of transition-metal- promoted carbon-phosphours bond formation.This thesis includes the following four parts:1. The development of new methods to synthesis of organophosphorus compounds were classified and summarized. The content mainly includes the introduction of new type reactions of transition-metal-promoted carbon-phosphours bond formation in recent years and also includes some new reaction of phosphours-heteroatoms bond formation. The reactions are classified by different reaction types.2. We developed a novel copper-catalyzed C-H bond oxdative phosphorylation reaction to form C-P bond. We employed a-amino ketones as substrate, diphenylphosphine oxide as the phosphorus sourse to construct C-P bond via transition-metal-catalyzed oxidative dehydrogenation coupling reaction. Based on some control experiments, we also proposed a possible reaction mechanism.3. We descried a silver-promoted P-radical cyclization reaction with the addition to isonitrile in detail. We use simple isonitrile compound as substrate to react with diphenylphosphine oxide. Many phosphorus-containing heterocyclic compounds were obtained through this tandem radical cyclization reaction.4. We presented in detail a highly efficient copper-catalyzed allylic C-H Phosphonation process. This method exhibits high regioselectivity and stereoselectivity. Various alkenes with useful functional groups are compatible in this transformation. Preliminary mechanistic studies reveal that the pH value and the loading of Ag-salt were the key factors to change the composition of products.