Synthesis Of ?-phosphonyl Carboxylate Derivatives Via P-H Insertion Reactions

Organophosphorus compounds play important roles in various fields,such as agrochemistry,pharmacy,materials science,and catalysis chemistry.Phosphorus is one of the most basic elements in life.C-P Bonds also exist in a large number of organisms,such as proteins and nucleotides,which constitute important organics of life.Transition metal-catalyzed carbene heteroatom-hydrogen bond(X-H)insertion reactions are direct and economical methods for the efficient construction of carbon-heteroatom(C-X)bonds.Due to the high coordination of phosphorus atoms,organophosphorus compounds are usually easy to poison metal catalysts,thus it is difficult to control the stereoselectivity of organophosphorus compounds-involved reactions.The research progress of P-H insertion reaction is relatively slow compared with other types of insertion reactions.Therefore,the efficient construction of the C-P bond via P-H insertion reaction of carbene under mild reaction conditions is still of high research value.The research work of this thesis includes the following two parts: one is to develop the synthetic method for ?-phosphonyl carboxylate derivatives by copper-catalyzed P-H insertion reactions of ?-carbonyl sulfoxonium ylides and H-phosphine oxides.The other is to develop the metal-free photocatalytic P-H insertion reactions of ?-diazocarbonyl compounds and H-phosphine oxides.In the first part of this thesis,we used safe and stable ?-carbonyl sulfoxonium ylides as metal carbene precursor.Sulfoxonium ylides are increasingly valuable metal carbene precursors with many advantages such as high thermal stability,easy crystallization,and no volatile gas produced during the reaction process.Copper complex catalysts have many advantages,such as cheap,easy to obtain,and so on.In this part,we have described the P-H insertion reactions of sulfoxonium ylides and phosphorus compounds catalyzed by copper complex.Under the optimal reaction conditions,?-phosphonyl carboxylate derivatives were synthesized in 41-93% yields.In the second part of the thesis,?-diazo carbonyl compounds,as carbene precursors,react with H-phosphine oxides to building C-P bonds with the460-470 nm blue light catalysis.In this method,this C-P bond forming reaction features many advantages such as metal-free,simple operation,mild reaction conditions.In this work,the synthesis of ?-phosphonyl carboxylate derivatives have been achieved by photocatalysis.The research in this thesis provides new ideas and practical methods for the construction of ?-phosphonyl carboxylate derivatives,which will promote the development of X-H insertion reactions,and provide a new approach to the construction of C-X bond in an efficient,cheap,environmentally friendly,and simple manner.