【作者】 安娜；

【导师】 乔仁忠；

【作者基本信息】 北京化工大学 ， 化学工程与技术， 2022， 硕士

【摘要】 含氧杂环化合物是一类具有重要生物学和化学意义的杂环化合物。其中,呫吨酮及其衍生物是一种在医药、荧光探针等方面应用潜力较大的具有生物活性的有机化合物。现有合成呫吨酮的方法大多存在取代基耐受性较差、反应条件剧烈、原料难以获得等缺点。因此寻找新的合成呫吨酮类化合物的方法,具有重要的意义。构建这类化合物的过程中,芳烃的C–H官能化是极为重要的一个方面。由N-磺酰基-1,2,3-三氮唑生成的α-亚氨基铑(II)卡宾配合物是一种重要的活性中间体,由于其良好的反应性,被用于合成各类生物学上具有重要意义的新型杂环化合物。通过N-磺酰基-1,2,3-三氮唑生成的α-亚氨基铑(II)卡宾配合物实现各种转化的方法也被认为是实现芳烃官能化的重要途径。本课题首次构建了一种简便、温和、可控的铑(II)催化N-磺酰基-1,2,3-三氮唑类化合物合成呫吨酮的方法。以良好的产率合成了16个连接有不同性质取代基的呫吨酮衍生物,证明了该方法较好的取代基耐受性。此外,用高分辨质谱、高效液相色谱、混合物核磁分析等方法,确定了这一反应过程中四环类中间体的存在,并据此阐释了该反应的环化/氧化机理。同时,在连接特定取代基的情况下,分离获得了这种新型四环类化合物的纯品。该四环类化合物是一种含有3,4-稠合二氢吲哚结构的杂环化合物,也具有重要的生物学意义。本课题合成的呫吨酮类化合物和新型四环类杂环化合物在医药和生物学方面具有重要的应用前景。本课题构建的高效且温和的芳烃C–H官能化的方法也为未来更多杂环化合物的合成提供了思路。更多还原

【Abstract】 Oxygen-containing heterocyclic compounds are a class of heterocyclic compounds with important biological and chemical significance.Xanthone and its derivatives are bioactive organic compounds with great potential in medicine and fluorescence probe.Most of the existing methods for the synthesis of xanthone have some disadvantages,such as poor tolerance of substituents,harsh reaction conditions,difficult access to raw materials,etc.Therefore,it is of great importance to find new methods for the synthesis of xanthones.In the process of constructing these types of compounds,the functionalization of aromatics is a very important aspect.The α-imino rhodium(II)carbene complex formed from N-sulfonyl-1,2,3-triazole is an important active intermediate.Due to its good reactiveness,it has been used to synthesize novel heterocyclic compounds of great biological significance.Various conversion methods of α-imino rhodium(II)carbene complexes formed by N-sulfonyl-1,2,3-triazole are also considered to be important ways to achieve arene functionalization.In this work,a simple,mild and controllable method for the synthesis of xanthone from N-sulfonyl-1,2,3-triazole compounds catalyzed by rhodium(II)was developed for the first time.16 xanthone derivatives with different substituents were synthesized in excellent yields,which proved that the method has good substitution tolerance.In addition,the existence of tetracyclic intermediate during the reaction was confirmed by high-resolution mass spectrometry,high-performance liquid chromatography and nuclear magnetic analysis of the mixture.Based on this,the annulation/oxidation mechanism of the reaction was explained.The pure product of the new tetracyclic compounds was obtained in the presence of specific substituents.The tetracyclic compounds we synthesized are heterocyclic compounds with3,4-fused dihydroindole structure,which also have important biological significance.Xanthones and the new tetracyclic compounds synthesized in this work have important application prospects in medicine and biology.The efficient and mild method of aromatics functionalization developed in this work also provides an alternative pathway for the synthesis of more heterocyclic compounds in the future.更多还原