Transition Metal-catalyzed Radical/radical Coupling Reaction And C?C Bond Cleavage Reaction

With the development of radical chemistry,the charm of radical chemistry is gradually known to chemists.In many areas of social demand,from agriculture to pharmaceuticals,etc.,all base on the development of organic chemistry.The use of free radical chemistry can greatly shorten the time for organic reactions and create opportunities for ideal synthesis.At the same time,one of the methods to increase the complexity of molecules is radical chain reaction,which can save chemists a great deal of time,and can be applied to the synthesis of complex organic compounds,pharmaceutical intermediates,etc.,for the development of a wide variety of organic synthesis methods.This article first briefly summarizes the development of metal organic chemistry and free-radical chemistry,and reviews the transition metal-catalyzed free radical coupling reaction and the C?C bond cleavage reaction.Based on the above summary,this article has developed the radical/radical coupling reaction of transition metal copper catalyzed and the transition metal-catalyzed nitrogen radicals in the C?C bond cleavage reaction.Related research has mainly achieved the following results:1.A new protocol for C-S bond formation was developed by selective radical cross-coupling between thiyl radical and isobutyronitrile radical.With this strategy,a series of valuable ?-alkylthionitriles derivatives were synthesized from basic starting materials.Preliminary mechanistic investigation was performed by EPR and XAFS,revealing that the transient thiyl radical could be stabilized by copper catalyst to a persistent one.Therefore,on the basis of persistent radical effect,selective radical/radical cross-coupling between the thiyl radical and isobutyronitrile radical was achieved successfully in this work.2.This work uses NFSI(N-fluorobenzenesulfonimide)to obtain nitrogen radicals under the action of transition metal,and in the presence of an oxidizing agent,using nitrogen radicals to complete C?C bond cleavage and further synthesize ketone compounds.The method not only develops a new way for C?C bond cleavage,but also synthesizes a series of ketone compounds with excellent yields,and has a variety of substrate types and is of great significance.