邻氨基苄氯在苯并杂环合成中的应用研究.pdf

中文摘要 摘 要 六元氮杂环作为核心结构骨架广泛存在于多种具有显著生物活性的天然产物 和药物分子之中。发展温和、绿色的合成方法来高效构建该类化合物显得尤为重 要。环化反应作为构建杂环化合物最有效的方法之一，受到了越来越多的关注。 本文基于邻氨基苄氯的性质，发展了碱促进下的环化反应，成功实现了两类苯并 六元含氮杂环的高效构建。 α β ①发展了碱促进下由邻氨基苄氯原位生成的环状 ，-不饱和亚胺与甲醛亚胺 前体1,3,5-三芳基六氢-1,3,5-三嗪的[4+ 2]环加成反应，以中等到优异的收率得到 结构多样性的四氢喹唑啉类衍生物。该合成方法具有反应条件温和、底物适用范 围广及操作简便等优点，此外，该反应可以放大到克级。 ②基于上述工作，发现了邻氨基苄氯可以在碱促进下发生分子内的环化反应， 通过对碱、溶剂等影响因素的考察，最终以中等到优异的收率合成了一系列结构 X 多样性的苯并噁嗪类化合物。通过核磁共振氢谱、碳谱、高分辨质谱、熔点、 - 射线单晶衍射方法，我们对产物结构进行了表征。 1,3,5 1,3,5 关键词：六元氮杂环；不饱和亚胺；邻氨基苄氯； -三芳基六氢- -三嗪； 环加成反应 I 英文摘要 Abstract Nitrogen-containing six-membered heterocycles as privileged scaffold are widely found in natural products and pharmaceuticals. Therefore, it is highly desirable to develop mild protocols to access heterocyclic compounds with biological activity. Among the established methods to construct six-membered N-heterocycles, annulation reactions are probably the most straightforward methods and received considerable attention.Based on theproperty of o-aminobenzyl chlorides, in thepresent dissertation, twokindsofsix-memberedN-heterocycleswereobtainedwithhigh efficiency. Wehave developed abase-promoted formal [4 + 2] cycloaddition ofin situ formed aza-o-quinone methides from o-aminobenzyl chlorides with hexahydro-1,3,5-triazines to synthesize a series of tetrahydroquinazoline derivatives in moderate to good yields. This protocol features mild reaction conditions, a wide substrate scope and good functionalgroup tolerance.Thereaction canbeperformed onthegram scale. Based on the previous wo