Amino Acids To Promote Cu-catalyzed Ullmann Coupling Reaction In The Synthesis Of Heterocyclic Compounds

This thesis describes the synthesis of functionalized benzimidazolones,benzimidazoloes and dibenz[b,f][1,4]oxazepin-11(10H)-ones via some CuI/aminoacid catalyzed reactions.The first part of this dissertation reports a procedure for the preparation ofbenzimidazolones via a domino process involving a CuI/proline-catalyzed C-Ncoupling reaction and an intramolecular amidation reaction. Both electron-rich andelectron-poor aryl halides could react with primary amines to give the corresponding1-substituted benzimidazolones in good to excellent yields. The simplicity of theprocess and the relative lack of methods to prepare benzimidazolones should renderthis method of great use to synthetic chemists.The second part of this dissertation demonstrates that NHCOR groups canprovide an ortho-substituent effect in CuI/proline catalyzed amination of2-haloacetanilides. Based on this observation, a novel and highly practical method forelaborating benzimidazoles is developed. Variation at the 1-and 2-positions of thebenzimidazole is possible when different primary amines are employed and withvariation in the amido groups of the 2-haloacetanilides. Moreover, in contrast to theexisting methods, our strategy allows the introduction of substituents in differentpositions of the benzimidazole phenyl ring. Thus, the present cascade process allowsthe assembly of a wide range of polysubstituted benzimidazoles.The third part of this dissertation illustrates a mild and efficient method for the preparation of dibenz[b,f] [1,4]oxazepin-11 (10H)-ones via a CuI/N,N-dimethylglycinecatalyzed intramolecular biaryl ether formation reaction, Good yields were only seenwhen electron-rich aryl bromides was used. Using the similar strategy we synthesized14-membered L, L-cycloisodityrosine subunit of natural product RP-66453, fromphenylalanine in 16ï¼…overall yield and nine steps.