One-pot Cascade Reactions For The Assembly Of Heterocyclic Compounds Via Copper-Catalyzed Cross Coupling Reactions

In the past decade, considerable progress has been made in the area of copper-catalyzed Ullman coupling reaction to form C-X (X=C, N, O, S etc.) bond. Because of its’low-cost, low toxicity and efficiency, the copper-catalyzed coupling has received much attention. It has showed broad application in many various synthetic fields, such as heterocyclic compounds, natural products, biologically active molecules, pharmaceuticals, polymers and so on.Recently, one-pot strategies for the syntheses of various useful heterocyclic compounds through copper-catalyzed coupling have aroused the interest of many groups because of their more convenient manipulations and good efficiencies.Our research group engaged in copper-catalyzed cross-coupling reaction. In this dissertation, we have systematically studied tandem rectation to construct heterocyclic compouds via Cu(I)-catalyzed cross-coupling process. The dissertation includes five parts. The first chapter reviews the progress of copper-catalyzed coupling reaction, and their participation in the tandem reaction progress to build heterocyclic compounds. In the second chapter, we studied copper catalyzed one-pot cascade synthesis of2H-1,4-benzoxazin-3-(4H)-ones. In the third chapter, we studied copper catalyzed domino synthesis of Quinoxalin-2(1H)-ones. In the fourth chapter,"copper-catalyzed cascade syntheses of2H-benzo[b][1,4]thiazin-3(4H)-ones and Quinoxalin-2(1H)-ones through capturing S and N atom respectively from AcSH and TsNH2" was studied. The last chapter reported "cascade syntheses of aza[2,1-b][1,3]-benzothiazine-5-one heteropolycyclic compounds from cyclic thiourea catalyzed by Cu(I)".In the second chapter, a novel and efficient one-pot cascade synthesis of2H-1,4-benzoxazin-3-(4H)-ones has been developed through copper-catalyzed coupling of o-halophenols and2-halo amides via SN2/coupling process. Various2H-1,4-benzoxazin-3-(4H)-ones with three points of substituted groups diversity in their scaffold have been synthesized conveniently.In the third chapter, we have developed domino SNAr/coupling/demesylation method, which relied on reaction of N-(2-halophenyl)methylsulfonamides with2-halo amides to assemble quinoxalin-2(1H)-one derivatives with diversity at three substituents on their scaffold.In the fourth chapter, an efficient copper-catalyzed cascade method has been developed to synthesize the2H-benzo[b][1,4]thiazin-3(4H)-ones from2-halo-N-(2-halophenyl)-acetamides1and AcSH via SN2/deacetylation/coupling process, and to synthesize the quinoxalin-2(1H)-ones from1and TsNH2via SN2/coupling/demesylation process.In the fifth chapter, we have developed effient cascade synthesis of aza[2,1-b][1,3]-benzothiazine-5-ones from cyclic thiourea and methyl2-iodobenzoate via C-S coupling/amide condensation process. Various aza[2,1-b][1,3]-benzothiazine-5-ones containing five, six, seven member ring and different substituents were obtained.