Study On Copper Catalyzed C-S Coupling Reaction For The Synthesis Of Nitrogen- And Sufur-containing Heterocyclic Compounds

The benzene fused heterocyclic compounds containing nitrogen and sulfur, such as benzothiazolethiones and 1,3-benzothiazines, are an important class of sulfur-containing heterocyclic compounds. These compounds have a wide research and application in natural products,pharmaceutical, pesticide, biological science, material science and other fields. Thus, development of general methods for the construction of these compounds is valuable. Recently, potassium sulfide has been widely investigated for introducing sulfur atoms into organic molecules.Compared with organic sulfides(thiols, sulfides), it has obvious advantages of low cost, available, low toxicity, relatively stability and easy operation. In this paper, general methods were developed for the synthesis of benzothiazolethiones and ring-fused 1,3-benzothiazines using potassium sulfide as sulfuration agent.This thesis includes the following three parts:Firstly, briefly introduction about the methods for synthesis of five or six ring benzoheterocycles containing nitrogen and sulfur, are demonstrated, which a variety of sulfuration agents are utilized in synthetic transformations to afford organosulfur compounds.Secondly, copper-catalyzed three-component efficient synthesis of benzothiazolethiones via multiple C-S bond formation was developed.Highlights is, the three component “one-pot”; K2 S as sulfuration agent Tosylmethyl isocyanide acts as a C1 source, So the method for the synthesis of benzothiazolethiones provides the new way which have potential value.Thirdly, a copper-catalyzed aerobic oxidative coupling reaction of potassium sulfide with N-substituted isoquinoline to the synthesis of ring-fused 1,3-benzothiazines was developed herein. This method provides an efficient approach to ring-fused 1,3- benzothiazines, Two C-S bonds are formed via a copper-catalyzed traditional cross-coupling reaction and an oxidative cross-coupling reaction.