Studies On The Direct Phosphorylation Of C-H Bond Induced By Radical Cation

Using the radical cation salt as the initiator to promote the aerobic oxidation of sp³C-H bond,the direct C-H phosphorylation was realized,providing a series ofa-aminophosphorate derivatives in high yields.In addition,we found that tert-butyl nitrite?TBN?as a cheap and commercially available reagent could also be efficiently used a to initiate the aerobic oxidation of glycine derivatives.The details were listed below:1.The aerobic oxidation of sp³ C-H bond in glycine derivative was efficiently achieved through radical cation salt initiated C-P formation,providing a series of?-amino phosphate derivatives.Mechanistic study revealed that radical and the corresponding iminium intermediates were involved in this reaction,and after nucleophilic addition by diethyl phosphite,the C-P bond was constructed smoothly.2.Using TBPA^+·/O₂ catalyst system,the reaction between N-benzyl anilines and dialkyl phosphites occurred smoothly,constructing C-P bond and synthesizing various?-amino phosphates.This reaction is superior in mild reaction conditions,fast reaction rate and high reaction efficiency.Through the value of kinetic isotope effect?KIE?shows that the cleavage of C-H bond is the rate-determining step.3.As a new catalyst system,TBN/O₂ can promote the sp³ C-H functionalization of glycine derivatives,giving a series of quinoline derivatives in high yields.The study of the reaction mechanism showed that TBN could react with oxygen,generating the peroxynitrite and tert-butyl radicals to promote the C-H bond activation.