Electrochemical Allylic Amination And Aziridination Of Olefins

Electricity is a renewable energy,which can be used to drive chemical transformations.The selectivities can be controlled by electrolyte,electrode material,and electrode potential.Organic electrochemical synthesis found wide applications in laboratory and industry,enabling challenging transformations in the green manner with high efficiency.Nitrogenous compounds is extensively occured in biomedical molecules,justifying efforts to develop various synthetic protocols.Olefins is an inexpensive and readily available material which were widely adopted as substrate in electrochemical reactions.Therefore,this paper first reviews the research of electrochemical reactions with olefins,and then explores the electrochemical amination of olefins with neither metal nor oxidant.This thesis includes the following chapters:1.Electrochemical Aziridination of Tetrasubstituted Alkenes with AmmoniaAmmonia is an ideal nitrogen source with 82%of nitrogen atom in terms of reactivity,safety and easy storage,acting as an ideal nitrogen source to synthesize amines.In this chapter,we demonstrated the first electrochemical protocol for directly introducing ammonia into tetrasubstituted alkenes in the absence of an oxidant and metal catalyst to afford the corresponding aziridines.By investigation with cyclic voltammetry and density functional theory calculations,we disclosed the combination of graphite felt as the anode material and Me OH as the solvent was the key to achieve the chemoselectivity.2.Electrochemical ring extension of aziridine for the synthesis of isoquinolinesIn this chapter,we reported the first electrochemical protocol for directly cleavage and recombination of olefins for the synthesis of isoquinolines with higher yields using the ring extension of aziridine,which was used multisubstituted indene and ammonia as the raw material,graphite felt as anode and silver sheet as cathode.The reaction is high atomic economy with quartic anodic oxidation,and its by-product is hydrogen.This method has been successfully applied to the synthesis of mosavirin.3.An Electrochemical Cinnamyl C(³_SP)-H Amination ReactionIn this chapter,an electrochemical cinnamyl C(³_SP)-H amination reaction in the absence of transition metal catalyst and oxidant was first reported,which was using oflens and carbonyl sulfamate as the raw material,graphite felt as anode and cathode.A series of terminal amine derivatives are prepared using this protocol and the sulfonyl group can be removed with basic hydrolysis.The choice of carbonyl sulfamate as nitrogen source is the key to achieve desired chemoselectivity.The reaction is suggested to proceed via a continuous anodic oxidation,deprotonation,anodic oxidation,and intermolecular nucleophilic addition pathway.