Base Promoted Synthesis Of Phosphorothioates From Simple Phosphorus Sources And Sulfur Reagents

Phosphonates are an important class of organic phosphine compounds.Among which sulfur-containing organic phosphine molecules have extensive applications in functional materials,pharmaceuticals,and agricultural chemicals.Therefore,the development of efficient and sustainable organic methodology for the construction of phosphine sulfur bonds is receiving increasing attention.The research progress of phosphorothioates was summarized in this thesis,and on this basis,we explored,designed,and developed new methods for the synthesis of asymmetric trithiophosphates and asymmetric dithiophosphates.The main contents of this thesis are as follows:1.Summarized the research progress in the synthesis of phosphorothioates,which can be divided into five parts:1)Synthesis of phosphorothioates promoted by bases;2)Synthesis of phosphorothioates catalyzed by metals;3)Synthesis of phosphorothioates promoted by oxides;4)Synthesis of phosphorothioates by photocatalysis or electrocatalysis;5)Synthesis of phosphorothioates by other methods.2.In this chapter,a series of asymmetric trithiophosphates were obtained by reacting with diphenyl disulfide compounds in the absence of metal,using potassium phosphate as a base and stable sodium phosphocyanate(Na OCP（dioxane）_2.5)as an inorganic phosphorus source in the air.This reaction does not require inert gas protection and the conditions are mild,which provides a new way for the synthesis of asymmetric phosphorotrithioates and realizes the conversion of inorganic phosphorus to organic phosphine.3.This chapter uses DBU as the base,trifluoromethanesulfonic anhydride as the activation reagent,and phenylhypophosphoric acid as the phosphorus source to react with thiophenol to obtain a series of asymmetric dithiophosphates,providing a new method for synthesizing asymmetric dithiophosphates.The structure of products were confirmed by ¹H NMR,¹³C NMR,³¹P NMR and HRMS...