咔唑并吡啶及咔唑并环戊酮类天然产物的全合成

发布时间：2018-05-02 15:52

本文选题：咔唑 + olivacine　；参考：《郑州大学》2017年硕士论文

【摘要】：咔唑类生物碱是一类比较重要的有机化合物,由于咔唑独特的结构,能在特定的位置加以修饰,而且咔唑的骨架合成有很多不同的方法,因此在咔唑的不同位点引入修饰,可以得到更多的咔唑类的衍生物。这类生物碱是具有刚性稠环的结构,表现出了特殊的光电性质,可以用于光电材料,也可以用于染料。此外该类的天然产物有很多具有很好的生物活性,比如抗癌活性,咔唑类化合物在医药领域的研究和开发备受关注。由于对该类化合物的需求越来越多,而传统的合成办法有比如反应温度高,使用重金属催化剂等诸多的限制,因此尝试用不同的合成办法来合成该类天然产物的研究具有很重要的意义。本文以吲哚三甲醛为原料经过Stobbe缩合,关环形成咔唑骨架,然后在咔唑A环上引入烯丙基,经过Claisen重排在苯环上引入烯丙基,以此为底物用发散法合成不同的咔唑天然产物。将羟基磺酰化,交叉偶联甲基化,双键氧化成醛,氨类化合物处理得到并吡啶酮环,同样磺酰化交叉偶联上甲基得到olivacine;双键氧化为酸,甲基化,Dieckmann缩合关环得到五元环,再脱羧反应得到clauemarazole D;将双键氧化为醛,醋酸铵处理关环得到吡啶酮环,磺酰化,还原得到lansine F,经硝酸铈铵氧化得到重要的中间体ellipticine quinone。其中有些生物活性比较好,有比较广阔的应用前景。
[Abstract]:Carbazole alkaloids are an important class of organic compounds. Because of the unique structure of carbazole, they can be modified in specific positions, and there are many different methods for the synthesis of carbazole skeleton, so the modification is introduced at different sites of carbazole. More carbazole derivatives can be obtained. This kind of alkaloids have rigid dense ring structure and exhibit special optoelectronic properties, which can be used in optoelectronic materials as well as in dyes. In addition, many of the natural products have good biological activities, such as anticancer activity, carbazole compounds in the field of medicine research and development has attracted much attention. Because of the increasing demand for this kind of compounds, the traditional synthesis methods have many limitations, such as high reaction temperature, heavy metal catalyst and so on. Therefore, it is of great significance to study the synthesis of this kind of natural products by different synthetic methods. In this paper, Stobbe condensation of indoletriformaldehyde was carried out to form carbazole skeleton, then allyl group was introduced into carbazole A ring and allyl group was introduced into benzene ring by Claisen rearrangement. Different carbazole natural products were synthesized by divergence method. Hydroxyl sulfonylation, cross-coupling methylation, oxidation of double bonds to aldehydes, treatment of ammonia compounds, synthesis of pyridinone ring, and the formation of olivacine from methyl on the same sulfonylation cross-coupling; oxidation of double bonds to acid, methylation of Dieckmann condensation ring to quintuple ring, After decarboxylation, clauemarazole D was prepared, and the double bond was oxidized to aldehydes, and ammonium acetate was used to close the ring to obtain pyridone ring, sulfonylation, reduction to obtain lansine F, and the important intermediate ellipticine quinone was obtained by cerium ammonium nitrate oxidation. Some of them have good biological activity and have a broad application prospect.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O629

【相似文献】