Transition Metal-catalyzed Azide And Alkyne Cyclization Reaction And Its Application In Organic Synthesis

Azide is a kind of very important organic intermediate. It can react with organic compounds to afford many nitrogen-containing compounds. The azide-alkyne cyclization reaction have been received much attention in recent years and widely found application in many fields. In this paper, we are interested in the transition metal-catalyzed azide and alkyne cyclization reaction and its application in organic synthesis, which including the following:In the first chapter, we have reviewed the recent studies about the azide-alkyne cyclization reaction and its application. We have summarized the Huigen reaction, such as the traditional Huisgen reaction, Cu(1)-catalyzed Huisgen reaction, and other metals-catalyzed Huisgen reaction to synthsize a variety of subsitituted triazoles. We have also summarized sulfonyl azide and alkyne-involved multi-component reactions, and intramolecular azide-alkyne cyclization reactions. In these reactions, Cu (1)-catalyzed azide and alkyne cycloaddition reactions (CuAAC) have been widely used in many fields, and we also have given a brief summary on its application.In Chapter II, First, we have reviewd the studies on the the chiral amino alcohols, which had been used in the borane-mediated reduction of prochiral ketones. We have synthesized 1,2,3-triazole-functionalized, C3-symmetric chiral amino alcohol catalysts via CuAAC reaction. Those catalysts have been used in the borane-mediated reduction of prochiral ketones. The results showed that the catalysts had good catalytic activity, and it could easily precipitate out from the reaction mixture and be reused after a simple washing and drying. The catalyst can be reused four times, without obvious decrease of catalytic activity.In Chapter III, we have developed the Ag-catalyzed intramolecular organic azide and alkyne cyclization to synthesize of 1,3-disubstituted isoquinolines or non-substituted isoquinolines. Firstly, we have reviewed the recent stuides on isoquinoline synthesis. Sencondly, the reaction conditions were optimized, and the scope of this reaction was investigated. Thirdly, we have also discussed the electronoc effect of substituents on the aromatic ring and proposed a resonable reaction mechanism. The results showed that the substituted isoquinoline could be synthesized in catalytic amount AgSbF6(20%) and 2 equiv TFA in the DCE at 80℃. The reaction afforded good to excellent yields under mild and simple conditions.