Studies On Constructing C-N And C-C Bonds By Transition Metal-catalyzed C-H Bond Activation

Transition metal-catalyzed C-H bond activation has been brought into sharp focus by many chemists,which is as a high atom economic,convenient,and excellent efficiency synthesis method.In the past decades,C-H bond functionalization has been developed rapidly.The reactive selectivity of C-H bond activation in reaction has been successfully solved with the aid of the directing groups.In this thesis,we developed the related methods for constructing C-N bonds and C-C bonds under the mild conditions,respectively.The contents are as following:The amidation of acetophenone O-methyl oximes and sulfonamides catalyzed by the transition metal iridium complex:In this work,we have explored iridium?III?-catalyzed directed ortho-C?sp²?-H bond amidation of arenes with sulfonamides.Compared with traditional method,C-H bond activation converts into C-N bond under the mild conditions,which avoids the pre-transformation of reactants,shortens the reaction steps and improves the synthesis efficiency.The reaction possesses the broad scope of O-methyl oximes and sulfonamides.All most substrates bearing various substituents could furnish the corresponding products with good yields.For example,acetophenone O-methyl oximes with F,Cl,Br,COOMe,CF₃,OMe and other substituents could achieve good yields,and sulfonamides with F,Cl,Br,COOMe,NO₂,CF₃,OMe,Me and other substituents also reacted well.It provides a convinent and effective method for the synthesis of substitued sulfonamides.And we designed relevant experiments and carried out a preliminary study on the reaction mechanism.The C-H bond of quinoline derivatives converted to C-C bond using transition metal copper and silver as catalysts:In this work,we have developed a mild protocol for the formation C-C bond of 8-aminoquinolines on the C5-position.In this transformation,1,3-dicarbonyl compounds and other compounds containing the active methylene coupled with 8-aminoquinolines using copper and silver salts as catalysts under air atomsphere.In this system,potassium persulfate is used as an oxidant.1,10-Phenanthroline is a ligand in this reaction.Finally,this reaction also provides a convinent and effective method for the synthesis of quinolone derivatives.