Studies On Iodine/TBHP Oxidative Coupling Reaction:for The Synthesis Of Phosphonamides And Aziridines

In recent years,the catalytic activity of iodine in many oxidative coupling reactions has been gradually discovered by scientists.Iodine or iodide could be combined with TBHP to form oxidative coupling system,which could easily and efficiently build chemical bonds.Compared with transition metal catalysis,this protocol has the advantages of environmental friendliness and easy operation.In this paper,two synthetic methods have been developed by using the oxidation system of I2/TBHP.The direct coupling of P(O)-H and N-H has been realized to prepare phosphonic amide compounds,and the intramolecular oxidation coupling could prepare aziridines compounds.The main research contents are as follows:1.Using ZnI2/TBHP oxidation system,P(O)-H and amines were directly oxidized and coupled,preparing phosphoamides in good efficiency at room temperature.The reaction was stereospecific.As we proposed,the iodine interacted with morpholine to form N-I compounds,and P(O)-H compounds as nucleophiles attacked N-I compounds to construct P-N bonds.2.Using ?-aminoketone as substrates,potassium carbonate as the base,the intramolecular N-H coupling proceeded smoothly to give azirines under KI/TBHP system.By adjusting the reaction temperature and the amount of base,the protected/unprotected azirines compounds could be selectively obtained.This method has the advantages of high efficiency,easy operation and good functional group tolerance.