Study On The Phosphorylation Reaction Of Aryl Sulfonate Compounds

Organophosphorus is one of the most important organic compounds.They are widely present in some natural products with biological activity and medical value.With the in-depth study of organophosphorus compounds,researchers also found that they play a huge role in the fields of medicine,pesticides,and new organic materials that are closely related to our lives,miking them become the indispensable organic compounds in chemistry-related fields.Due to the importance of organophosphorus compounds in modern chemistry,organophosphorus compounds have attracted great interest from researchers,and it is particularly important to develop simple and efficient synthetic methods.However,traditional synthetic methods often require the use of high-cost and toxic phosphorus reagents and relatively expensive metal catalysts,or the reaction conditions are harsh.Therefore,from the perspective of low cost and environmental friendliness,the use of practical,safe and low-toxic phosphorus reagents,or cheap and readily available starting materials to achieve the synthesis of organophosphorus compounds has more advantages and significance than traditional methods.The main research contents of this paper are as follows:1)We have developed a method for the formation of C（sp²）-P bonds via the cross-coupling of aryl fluorosulfonates with phosphinates or diarylphosphines under the catalytic system of Ni Cl₂ and Xantphos.The synthesis of aryl phosphine oxides and aryl phosphate was achieved without the use of expensive metal catalysts and toxic starting materials.This catalytic system allows a variety of phenols with diverse functional groups to transform into aryl phosphine oxides and arly phosphates with good yields,and the late-stage conversion of estrone was achieved.In addition,a probable mechanism of this coupling reaction was also proposed;2)We have developed a simple method for the formation of S-P（O）bond between R₂P（O）H and arylsulfinates,arylsulfinates（or sodium salts）under metal-,external reducing agent-,and halogen-free conditions.The method is easy to operate and can be carried out under open conditions.At the same time,the reaction is fast and efficient,has a wide range of substituent compatibility,and is also compatible with water as a solvent.The realization of gram-scale synthesis makes it more attractive in the preparation of organic thiophosphates.