Study On Anthranils Involved C-N Bond And C-C Bond Formation

The development of new methods for chemical bond formation is one of the core issues in organic chemistry.Nitrogen containing compounds,especially N-heterocycles,are widely applied in fine chemicals such as drugs,materials,dyes and so on.In recent years,transition metal-catalyzed C-H bond activation has attracted extensive attention of organic chemists,which avoids the pre-functionalization of substrates and allows the directly use of C-H bonds Therefore,the C-H bond activation strategy can greatly improves the synthetic efficience.In particular,transition metal-catalyzed amination of C-H bond has been rapidly developed,which becomes a powerful tool for the synthesis of nitrogen compounds.The discovery of new aminating reagents for C-H amination reactions plays a key role in the development of this type of reaction.In this thesis,anthranil（also known as 2,1-benzoisoxazole）was used as aminating reagent in C-H amination reaction with–COOH as a directing group for the efficient construction of nitrogen-containing compounds such as o-aminobenzoic acid derivatives and polysubstituted quinolines.In addition,we also disclosed that trifluoromethanesulfonic anhydride could activate anthranils by enhancing its electrophilicity,and a cross-dehydrogenation-coupling（CDC）reaction of anthranils and electron-rich arenes was achieved by using trifluoromethanesulfonic anhydride as a promotor...Overall,this thesis mainly studies the reaction of anthranils-in the construction of C-N bond and C-C bond.The main contents of this thesis include:Chapter one:In this paper,The introduction systematically introduces the reaction properties of anthranils,as well as the electrophilic amination reaction and hydrocarbon amination reaction that aniline anhydride has participated in in recent years..Chapter two:Rh（III）-Catalyzed Selective ortho-C-H Amination of Benzoic Acids with Anthranils:An efficient rhodium（III）-catalyzed Csp²-H amination of benzoic acid with anthranils to synthesize o-aminobenzoic acid derivatives was realized.All kinds of benzoic acid and anthranils can be smoothly adapted to the reaction,and o-aminobenzoic acid derivatives with medium to high yield were obtained.The weakly coordinated carboxyl group,as the guide group,further converted to ester group after promoting the first step of hydrocarbon amination.The reaction is characterized by good tolerance to functional groups,mild conditions and simple operation.The potential of this method was demonstrated by the synthesis of various useful heterocycles and derivatives.Chapter three:Rh-Catalyzed C-H Amination/Annulation of Acrylic Acids and Anthranils by Using-COOH as a Deciduous Directing Group:We have developed a rhodium catalyzed C-H amination/cyclization reaction of acrylic acid and anthranils to synthesize various substituted quinoline derivatives.Here,the weak coordination COOH guiding group is used as the non trace oriented group,which can be removed without trace in the cyclization reaction.Under mild reaction conditions,different kinds of multiple substituted quinoline were obtained by using simple H₂O and CO₂ as by-products.More importantly,we have obtained various quinoline derivatives in good yield,including valuable 1,2,3,4-tetrahydropacridine compounds（the core skeleton of the drug tacline）.Chapter four:Trifluoromethanesulfonic anhydride promotes the cross dehydrogenation coupling reaction of anthranils and electron-rich aromatic hydrocarbons.This part of the work verified our idea of using trifluoromethanesulfonic anhydride to enhance anthranilin anhydride,and initially realized the cross-dehydrocoupling reaction of anthranilin and electron-rich aromatic hydrocarbons promoted by trifluoromethanesulfonic anhydride,and efficient construction 3-aryl substituted anthranilic anhydride derivatives.