| The oxidation of tertiary amines is a significant topic in organic chemistry in recent years.The a-C-H activation of tertiary amines has been widely reported,including the Cross Dehydrogenation Coupling Reaction which is widely accepted.Among them,the oxidative phosphorylation and amidation of a-C-H are of great significance.Constructing N-C-P bonds or synthesizing a-aminophosphonate and other phosphorylation products is an improvement of the organic phosphorus compound library.Due to the wide application of organophosphorus compounds,green and efficient synthesis of organophosphorus compounds is the unremitting pursuit of organophosphorus chemists.The amidation of tertiary amines is not only the development of functionalization of tertiary amines,but also an important method to synthesize complex or novel amides.Exploring the construction of N-C-N bond is also the pursuit of chemists.C-N bond is an important chemical bond of many natural products or artificial functional molecules.Therefore,enriching compounds containing N-C-N bond has theoretical and potential application significance.Over the years,with the development of many fields of organic chemistry,consequently,the a-functionalization of tertiary amines has been continuously promoted.Chemists have developed transition metal catalysis,photocatalysis or metal free reaction,which has made this field active.This paper describes in detail the Cross Dehydrogenation Coupling reaction which was catalyzed by transition metals or promoted by organic oxidants,and studies the synthesis of a-aminophosphonates and amides from various tertiary amines and phosphorylation reagents or acylation reagents.The chemical bonds of N-C-P and N-C-N were constructed.1.A general method for the synthesis of a-aininophosphonate was developed.The general method includes two parts.Method(A)could be described as follows.The products were obtained by the reflux of tertiary amine and dialkyl phosphite in acetonitrile for 16 hours,using cheap and economical Co(OAc)2·4H2O as catalyst,NHPI as co-catalyst,air as oxidant.And the reactions were operated simply with high yield.Method(B)was a metal-free synthetic reaction.The products could be obtained by heating reaction of tertiary amine and dialkyl phosphite for 16 hours with TBHP as oxidant and acetonitrile as solvent.The applicability of the two general methods was highly consistent,so parallel studies were conducted at the same time.Aliphatic and aromatic tertiary amines could be used as amine sources simultaneously and efficiently,and it was the first reported method to synthesize a-aminophosphonate from aliphatic tertiary amines.2.A new strategy for the synthesis of N-((methyl(phenyl)amino)methyl)amides had been developed.20 kinds of amide compounds including A;,-((methyl(phenyl)amino)methyl)benzamide were synthesized by using nitrile as amidation reagents instead of traditional amides and other substrates.The method used CLul as catalyst,N-hydroxyphthalimide as co-catalyst,TEMPO as oxidant,toluene as solvent,tertiary amines reacted with nitriles in air at 100 ℃ for 16 hours to obtain the products.After optimizing the reaction conditions,the applicability of functional groups was studied,and the ideal yields up to 98%were obtained. |
