8-aminoquinoline-guided Palladium-catalyzed Directly Arylation Sp~3 Carbon-hydrogen Bonds

Carbon-hydrogen bond is the most widespread group in organic compounds of the nature.To constuct new carbon-carbon bonds,the most simple and effective way is from the C-H bond point of view.Selective activation and functionalization the inert carbon-hydrogen bonds,which is the most economical way,is undoubtedly one of the most effective methods for the preparation of functional molecules.A wide variety of catalytic functionalizations of C(sp2)-H has already been developed to date and have had a significant impact in the field of organic chemistry.It can now be said that it is no longer difficult to develop the functionalization of C(sp2)-H bonds.In this sense,the catalytic functionalization of C(sp2)-H bonds is now recognized as one of general organic synthetic reactions available to organic chemists.Because of this,much attention is currently focused on the functionalization of C(sp3)-H bonds,which continues to be a challenging issue.The paper is focused on C(sp3)-H bonds activation,mainly describes the transition metal palladium-catalyzed sp3 C-H bonds?-arylation of amide derivatives.The content of this paper is as follows:The opening chapter is a review to sumIarize the current progress of sp3 C-H bonds arylation both domestic and foreign.And then it respectively introduces the application of precious metals(Pd,Rh,Ru)and base metals(Fe,Ni)in this field.In the second part,We have developed a method for directed group-auxilia-ry,palladium-catalyzed arylation of sp3 C-H bonds system.The method empio--ys a 8-aminoquinoline amide substrate,aryl iodide coupling partner,Bis(acetoni-trile)-dichloropalladium catalyst,an inorganic base,and in mesitylene without e--xclusion of air or moisture.This transformation has good functional group com-patibility and can serve as a powerful synthetic tool for late-stage C-H arylati-on of complex compounds.At the beginning of the third part,it briefly introduces the progress of sp2 carbon-hydrogen bonds arylation in recent years.we extend the same catalytic system to sp2 carbon-hydrogen bond arylation,to our surprise,the results are also very good.This means that we have broken through a catalytic system which can only be applied to a type of substrate in the past.The last part is about mechanism part,it describes the correct designing method for deuterated experiments.The KIE experiments show that the C-H bond activation is not the rate-etermining step.Combined with the previous condition optimizing section,we conclude that the mechanism of this reaction is "Base assisted concerted metalation/deprotonation".