Electrochemical Enables Functionalization Of Electron-rich Arenes And Heteroarenes

With the rapid development of the global economy,the process of industrialization has greatly accelerated,and environmental issues have become increasingly prominent.In order to protect the natural environment in which humans live,it is necessary to avoid or reduce pollution from the source.For this reason,in recent years,scientists have been working hard to explore the use of more green chemistry to synthesize new compounds.Organic electrochemical synthesis is a very efficient,simple and green new organic synthesis method.Compared with traditional chemical synthesis,it generally requires equivalent or excess oxidation/reducing agents,which results in the production of a variety of toxic chemical waste and increases environmental costs.Organic electrochemical synthesis is achieved directly through the anodic oxidation and cathodic reduction of reactants.The reaction,the reaction conditions are more mild,the operation is simple and convenient,and the reaction efficiency is relatively high.It is a new synthetic method in accordance with the concept of green chemistry.In recent years,more and more chemists have paid attention to it,and it has become a popular and widely used method in the field of organic synthesis.This thesis focuses on electrochemical enables functionalization of electron-rich arenes and heteroarenes.The full text includes four parts.Firstly,it is a detailed reviewing of the development history,theory,device,application method and advantages and disadvantages of organic electrosynthesis.Then involves the application of electron-rich arenes and heterarenes under the electrochemical method.The second part involves external-oxidant-free electrochemical oxidative trifluoromethylation of arenes.In the third part involves electrochemical oxidative N1/C2 region-switchable phosphorylation of free indoles.In the fourth part involves electrochemical enables azo of aniline.The main research results are as follows:(1)External-oxidant-free electrochemical oxidative trifluoromethylation of arenesA novel electrochemical synthesis method was established for the synthesis of trifluoromethylation of arenes.The method is carried out under simple constant current electrolysis conditions,requiring only a single-chamber electrolytic cell,without any additional catalyst,using sodium trifluorosulfinate as the CF₃source,and arenes as free radical acceptors.The target product was efficiently produced,the trifluoromethylation reaction of SP₂carbon was successfully realized,and a series of trifluoromethylation of arenes'compounds were synthesized.(2)Electrochemical oxidative N1/C2 region-switchable phosphorylation of free indolesFor the first time,an efficient and green electrochemical synthesis method was discovered,which realized the selective phosphorylation of indole N1 and C2.The method is performed under simple constant current electrolysis conditions,requiring only a single-chamber electrolysis cell,using triethyl phosphite and its derivatives as the organic P source,and free indole as the free radical or nucleophile receptor,Using the change of the electrolyte,electrochemically selective generation of different active species,the selective phosphorylation of the indole N1/C2 position was successfully achieved.(3)Electrochemical enables azo of anilineFor the first time,a simple,green electrochemical synthesis method was discovered,which achieved the azo reaction of aniline.The method is carried out under simple constant current electrolysis conditions.It only requires a single-chamber electrolytic cell,using aniline and its derivatives as substrates,pyridine as a base,hexafluoroisopropanol as an additive,and KI as an electrolyte and catalyst.The azo reaction of aniline was successfully achieved.