新型四炔模块苯炔前体高效构建咔唑类衍生物  

Efficient Construction of Carbazole Derivatives via New Benzyne Precursors of Four Acetylene Modules

作　　者：陈钊[1] 单威[1] 尹军[1] 余广鳌[1] 刘盛华[1] 

机构地区：[1]华中师范大学化学学院农药与化学生物学教育部重点实验室,武汉430079

出　　处：《化学学报》2015年第10期1007-1012,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.21272088;21472059;21402057);武汉市学科带头人计划(No.201271130441)资助~~

摘　　要：采用卡迪奥-肖德凯维奇偶联反应合成了一系列的四炔类的化合物,随后利用这些新型四炔模块苯炔前体高效地合成了一系列咔唑类衍生物.此外,银具有很好的催化活性,当加入催化量的Ag NO3到反应体系中时,通过一步反应能够获得同时含有咔唑环和吲哚环的多元杂环化合物.更重要的是,这些反应具有很高的产率.此外,这类反应的底物适用性是非常广的.并且提出了涉及到Ag NO3催化的N—H插入反应的可能的机理.Benzyne is one of very important reactive intermediates in organic synthesis, and has been comprehensively utilized as a building block in organic synthesis. However, traditional synthetic methods need to use harsh reaction condition, which has limited its practical application. With the emergence of moderate preparation method, benzyne has attracted considerable attentions from synthetic chemists. Latest results indicate that benzyne can be effectively generated by using some special intermediates containing three or four acetylene motifs, which called the hexadehydro-Diels-Alder （HDDA） reaction. This thermal cycloisomerization of a triyne precursor constitutes a reagent and byproduct free method for making benzyne intermediates of considerable structural complexity. On the other hand, carbazole and its derivatives is one very important type of nitrogen-containing aromatic heterocyclic compounds. They are used as pharmaceuticals, agrochemicals, dyes, pigments, light-emitting photosensizer, charge/hole transport material and photovoltaic and display devices, etc. Various functional groups can be easily introduced into carbazole ring through structural modification. Develop new synthetic methodology for the synthesis of carbazole and its derivatives is very important. In this paper, we took advantage of the hexadehydro Diels-Alder reaction ofbis-1,3-diynes to generate arynes and used them for an intramolecular nucleophile addition reaction to generate various carbazole derivatives. A series of four acetylene-containing compounds were synthesized through the corresponding Cadiot-Chodkiewicz coupling reaction in good yields. The corresponding carbazole derivatives were received in good yields after heating benzyne precursors of four acetylene modules in toluene at 90 ℃ for 5 h. These reaction exhibited very high efficiency as well as wide substrate scope. In addition, we found that the carbazole ring and indole ring were formed simultaneously in one step with using AgNO3 as catalyst. The possible mechanism of

关 键 词：苯炔 四炔模块 咔唑 杂环化合物 咔唑类衍生物 

分 类 号：O626[理学—有机化学]