Study On C(sp~3)-H Bonds Functionalization Adjacent To Nitrogen Atom And Dioxygenation Of Alkenes

Oxidative coupling reactions are the process that combines two or more organic chemical by the coupling in oxidative dehydrogenation manner.Oxidative coupling reactions have attracted considerable attention due to high-efficiency,environment friendliness and atom economy.The continuous investigation of new oxidative couplings still have a meaningful academic value for enriching the current content of oxidative coupling.The dissertation select materials containing C(sp3)-H bonds functionalization adjacent to nitrogen atom such as N,N-dimethylanilines and N-aryl tetrahydroisoquinolines and alkenes,which are converted into a series of compounds with potential biological activities through metal or metal-free catalyzed oxidative couplings,in which C(sp3)-H bonds functionalization are realized by catalytic activation of their C(sp3)-H bonds.In addition,the dioxygenation of alkenes are also studied in detail.This dissertation consists of four sections,the details are as follows:In the first part,the recent research progress on C-H bond functionalization adjacent to nitrogen atom has been surveyed.The present research status of C(sp3)-H and C(sp2)-H bonds functionalization are described.Additonally,the novelty of this dissertation is described in this part.In the second part,a new oxidative carbene coupling(OCC)has been developed.In this reaction,N,N-dimethylaniline,?-diazo aryl ketones and carboxylic acids are selected as reaction substrates,which underwent Cu-catalyzed three-component coupling in the prensence of tert-butyl hydroperoxide(TBHP)to access a series of structurally diverse ?-oxy-?-amino ketone derivatives.Alternatively,N-methyl anilines was served as replacement of carboxylic acids,which underwent a similar three-component coupling in the prensence of Fe(II)-catalyst and TBHP to give ?,?-diamino ketone derivatives.The generalization of the reaction is investigated and alkylation of C(sp3)-H bonds functionalization adjacent to nitrogen atom is realized.Several controll experiaments reveal that the reaction is involved in carbene migration insertion process under oxidative conditions.In the third part,a new Cu-catalyzed dediazotizated [4+1] cyclization is developed.The Cu-catalyzed reaction between N-aryl tetrahydroisoquinolines and ?-diazo aryl ketones are occurred,which undergo dediazotizated [4+1] cyclization and dehydrogenated aromatization to synthesize a range of highly substituted isoindolo[2,1-a]quinolines with realization of C(sp3)-H bonds functionalization adjacent to nitrogen atom.The electronic nature of substituents resided in the phenyl ring of ?-diazo ketones have an important impact on the yield of reaction when the reaction scope is expanded.The donating groups lead to a higher yield than withdrawing groups.On the basis of literature investigations,a reasonable mechanism is proposed.In the fourth part,a metal-free dioxygenation of alkenes is described.The reaction of alkene with 1H-benzo[d][1,2,3]triazol-1-ol and DDQ in dichloromethane at room temperature lead to the highly efficient synthesize of 4,5-dichloro-3-hydroxy phthalocyanine derivatives.During this process,DDQ play dual roles both a dehydrogenation reagent and a reaction component for the dioxygenation of alkene.The reaction have easy availability of starting materials,the broad scope of reaction and mild reaction condition as well as atom economy,providing a highly efficient synthetic method for the construction of 4,5-dichloro-3-hydroxy phthalocyanine derivatives.