Study On Organocatalytic Asymmetric Inverse-Electron-Demand Aza-Diels-Alder Reactions And[3+3]-Annulation Reactions

In recent years,the asymmetric synthesis of organic catalysis has been developed rapidly,providing an important method for the construction of chiral compounds in a simple,efficient and rapid manner.The Diels-Alder reaction and the [3+3]-annulation reaction are important methods for the construction of six-membered carbocyclic or heterocyclic rings,the asymmetric synthesis of chiral six-membered skeleton via organocatalyzed Diels-Alder reaction and [3+3]-annulation reaction often shows significant advantages.This thesis is on the subject of organocatalyzed asymmetric aza-Diels-Alder reaction and [3+3]-annulation reaction,the application of oranocatalysis in the construction of multi-ring system was explored.This thesis is divided into the following three chapters.The first chapter: The development of asymmetric aza-Diels-Alder reactions.Based on the different catalytic modes,the research of asymmetric aza-Dilder-Alder reaction in recent years is summarized in this paper.The second chapter: Study on organocatalytic asymmetric inverse-electron-demand aza-Diels-Alder reactions based on azlactones.Azlactone derived enolate are often used as nucleophilic species in organocatalyzed asymmetric synthesis,but only a few examples of inverse-electron-demand oxa-Diels-Alder processes with azlactone-enolates as dienophiles have been reported.In this paper,azlactone derived enolate was used as dienophile,an enantioselective inverse-electron-demand aza-Diels-Alder reaction of saccharin-derived 1-azadienes and azlactones was developed via oaganocatalysis,which furnished a chiral tricyclic architectures.The third chapter: Study on organocatalyzed asymmetric [3+3]-annulation reactions based on indoline-2-thiones.Organosulfur compounds play an important role in biological and medicinal chemistry.Among them,thiopyrans skeleton as the core structure of many drug molecules,its asymmetric synthesis is of great significance.We have developed an asymmetric [3+3]-annulation of indoline-2-thiones and 2-nitroallylic acetates by the use of bifunctional organic catalyst,and provided an avenue to the asymmetric synthesis of the thiopyrano-indole skeleton bearing potential drug activity.