The Effect Of L-proline Ligand Trifluoroacetyl Amino Ortho Effect And Jointly Promote The Cui Catalyzed Ullmann Coupling Reaction In The Synthesis Of Heterocyclic Compounds

Copper-catalyzed Ullmann type cross-coupling reactions have been greatly developed in the last century,especially with the development of the catalysis system which intergrading ligands with catalyst during the last 10 years.How to use Ullmann type reaction to synthesize bioactive heterocycles has become one of the research focuses.In this dissertation,we emphasized on the application of ligand and ortho-substituent promoted/copper catalyzed Ullmann type reactions.We studied some tandem processes in which Ullmann reactions participated of preparing bioactive heterocyclesIn the second chapter of this dissertation,we studied the process of preparing pyrrolo[1,2-a]quinoxalin-4(5H)-ones via a copper catalyzed Ullmann type reaction promoted by amino acid ligand and ortho-substituent.We got the optimized reaction conditions using the reaction of methyl 1H-pyrrole-2-carboxylate with 2-iodotrifluoroacetylaniline.Then we tested these conditions by using different 1H-pyrrole-2-carboxylates and 2-halotrifluoroacetylanilines as substates,and obtained the target products successfully.If replacing 2-halotrifluoroacetylanilines by 2-bromo-3-trifluoroacetylamidopyridines,we could get pyrido[3,2-e]pyrrolo[1,2-a] pyrazin-6(5H)-ones.Otherwise,if replacing methyl 1H-pyrrole-2-carboxylate by methyl 1H-indole-2-carboxylate,we could obtain indolo[1,2-a]quinoxalin-6(5H)-ones. We also proposed the reaction mechanism to explain the phenomenon which we observed. In the third chapter of this dissertation,we firstly studied the process of preparing 2,3-dihydro-1H-carbazol-4(9H)-ones via a copper catalyzed Ullmann type reaction promoted by amino acid ligand and ortho-substituent.We optimized the reaction conditions using the model reaction of 2-iodotrifluoroacetylaniline with cyclohexane-1, 3-dione.Then we tested other aryl iodides under these optimized conditions and got the target products successfully.To bromides,we can obtain the products with middle to excellent yield only need to increase the amount of cyclohexane-1,3-dione to 1.5 equiv and rise the temperature to 50℃for some of the bromides.Secondly we replaced cyclohexane-1,3-dione by cyclopentane-1,3-dione to study the synthesis process of 2,3-dihydrocyelopenta[b]indol-1(4H)-ones.We got the optimized reaction conditions using 2-iodotrifluoroacetylaniline and cyclopentane-1,3-dione as the reaction substrates.Under these optimized conditions,we tested the aryl halides and discovered that the reaction temperature must be at 50-70℃to make the coupling reaction operate successfully for all bromides and some of the iodides.Because of acid hydrolysis,we can only get the products when the substrates were stable in acidic condition.We also proposed the reaction mechanism to explain the phenomenon which we observed.