Study On The Cycloaddition/Oxidation Reaction Of [3+2] With Activated Alkene And Organic Azides

1,2,3-triazoles are important class five-membered rings heterocycles compounds with wide applications in medicinal,material and synthetic organic chemistry.Especially in medicinal,some 1,2,3-triazoles show a broad spectrum of biological activities such as antifungal,antiviral,anti-allergic,anti-HIV,and antimicrobial activities.With the development of click chemistry,many of different 1,2,3-triazoles have been reported.However,compared with traditional 1,2,3-triazoles,the synthesis of functional 1,2,3-triazole is more difficult.The synthetic methods for these compounds are not so much.Activated alkene origated from many compounds,but there are few based on avtivated alkene for the synthesis of functional 1,2,3-triazoles.These methods ultized the functional elimination to synthesize no-functional1,2,3-triazoles.So in this thesis,we design a highly effectient method to synthesize functional 1,2,3-triazole compounds by using activated alkene and organic azides.At the same time,the selectivities of the reaction were investigated.The involved oxidative process overcomes the elimination functional group for general cycloaddition of activated alkene with organic azides,which shows a high atom economy and potential applications.By the way,the machanism of reaction have been studied.The thesis is divided into the following sections:In the first chapter,the synthetic methods of 1,2,3-triazole compounds and their applications in the field of chemistry,materials,biology,medicine were reviewed.In the second chapter,the synthesis of 1,4?-NO₂?,5-trisubstituted 1,2,3-triazoles compounds was reported.This reaction sequence has a broad substrate scope and affords NO₂-substituted 1,2,3-triazoles with high regioselectivities and in good to excellent yields.In the third chapter,the mechanism of synthetic methods for1,4?-NO₂?,5-trisubstituted 1,2,3-triazoles compounds was studied.The involved oxidative process overcomes the elimination of HNO₂ for general cycloaddition of nitroolefins with organic azides,which shows a high atom economy and potential applications.A plausible mechanism was reported.In the forth chapter,an efficient Mn?III?-mediated coupling reaction of sodium sulfinates with nitro-olefins has been developed.This reaction proceeds in a mild and open-flask condition to afford?E?-vinyl sulfones with high regioselectivities in good to excellent yields.And we tried to the methods for the synthesis of4-sulfonyl-1,2,3-triazoles.In the fifth chapter,the mechanism of synthetic methods for?E?-vinyl sulfones was studied.The control experiments revealed that this transformation involved a radical process.A plausible mechanism was reported.In the sixth chapter,we summarized the research and plan to set up the next goal.