Photoredox Catalyzed Smiles Rearrangement Reaction

Smiles rearrangement is a reaction that uses aromatic groups as nucleophilic reagents to access the migration of aromatic groups through a certain intramolecular rearrangement process.As a kind of ancient and long history reaction,since its discovery,with its unique reaction process and reaction mechanism,it has always provided chemists with a special and efficient way to achieve the synthesis of complex molecules,especially the arylation reaction at key positions.With the continuous development and innovation of chemical research and theory,Smiles rearrangement has always been active on the experimental stage of chemists in different forms.In this paper,N-sulfonylamide substrates are taken as the research object,the aromatic group migration strategy of intramolecular Smiles rearrangement reaction is adopted,and the visible light redox catalytic reaction is used to successfully realize efficient synthesis of α-aryl amide molecular skeleton;In addition,we also explored the asymmetric study of Smiles rearrangement.The specific content is divided into three parts to discuss.In the first part,the reaction mechanism and process of classical Smiles rearrangement reaction are briefly introduced;Then,according to the history of Smiles rearrangement and the different forms derived in the development process,the application of Smiles rearrangement in organic synthesis is introduced from many aspects;Finally,the uniqueness of Smiles rearrangement in the construction of complex molecular reactions is summarized,and the problems in the current development process of Smiles rearrangement are analyzed in depth.In the second part,due to the important roles the α-aryl amides play in pesticides,drugs and biomolecules,first,the synthesis methods of these skeletons are summarized and analyzed.We find that the construction of α-aryl amides by metal-free catalytic systems under mild conditions is still a challenge in this field.Based on this,in this part,N-sulfonylamide is used as the reaction substrate,the new efficient organic photocatalyst developed by our research group is used,and the strategy of combining visible-light photocatalysis with Smiles rearrangement is successfully realized under mild conditions to access α-aryl amides.Subsequently,the universality of the substrate of the reaction was investigated,and the relevant exploration of synthesis and application was carried out.In the third part,as we all know,asymmetric synthesis has always played an extremely important role in organic synthesis.In this part,the development and research status of asymmetric synthesis are briefly summarized;Subsequently,through literature research,we find that the Smiles rearrangement involving asymmetric processes is almost blank in this field.Based on this,the experimental part of this chapter is an attempt to conduct asymmetric Smiles rearrangement reactions using two strategies,catalytic asymmetry and induced asymmetry.