Asymmetric Transformation Of Aryl Diazo Esters Between Allyl Azides And Alkyl Azides

In recent years,related literature studies on these kinds of azides have been reported.Allyl azide,as a special type of azide,can spontaneously carry out intramolecular[3.3]-σ rearrangement,that is,Winstein rearrangement.A series of azide mixtures are usually obtained,which limits the application of these azides in organic synthesis.In this thesis,based on the previous and our research results on the condensation of alkyl azide and diazo ester,and the intermolecular[2,3]-σ rearrangement of allyl heteroatom compound and metal carbene,the combination of allyl azide and α-diazo ester was successfully designed and realized.That is,the intermolecular[2,3]-σ rearrangement of allyl azide and α-diazo ester;he intermolecular desymmetrization condensation of alkyl azide and diazo ester was studied based on organic azide.The first part of the paper introduces the research status of the rearrangement and reaction of allyl azide,mainly from two aspects.If the olefin double bond is used as the reaction site,it can selectively undergo dihydroxylation,epoxidation and other types of oxidation reactions;if azide is used as the reaction site,it can be selectively converted to imines,amines,nitriles and amides,and intermolecular cycloaddition reaction with alkynes,olefins and nitriles.In the second part of the thesis,the intermolecular[2,3]-σ rearrangement of allyl azide and α-diazo ester was studied.Using 1,3-diphenyl allyl azide and diazomethyl phenylacetate as standard substrates,mental catalyst,catalyst loading,solvent,temperature,method of adding substrates were selected,the efficient conversion of the reaction was achieved under 20℃ with Rh₂（esp）₂ as catalyst and decane as solvent.Nine products were prosperously prepared with a yield of 45%to 76%,and the value of dr only 1:2.Using chiral Rh₂（S-TCPTTL）₄ as catalyst,the rearranged product was obtained with a high conversion rate of 99%,but the chiral control ability was moderate,with the value of 50%to 60%ee.In the chiral system of chiral ligand CuPF₆（MeCN）₄/ligand,the conversion efficiency was low,the yield was 15%to 56%,and the value of ee was 30%to 70%.In the future,we will carry out in-depth research on different chiral catalytic systems in order to achieve high yield and stereoselectivity at the same time.In the third part of the thesis,the intermolecular desymmetric condensation of dialkyl azide with diazo ester was studied.Using 2-phenyl-1-diazopropane and diazo methyl phenylacetate as template substrates,only trace conversion can be achieved under chiral copper/ligand catalysis system,and the product is almost chiral;the overall efficiency and chiral control of the reaction in chiral rhodium system are low,the highest yield is only 36%,and the ee value is only 10%.The diazide substrate was redesigned and tried to react,and the results showed that the new substrate could not have this condensation reaction.In the future,we will explore the asymmetric condensation reaction of different types of alkyl diazide substrate.