《在β-内酰胺、氧代吲哚及刺桐类生物碱合成中的应用研究》由会员分享，可在线阅读，更多相关《在β-内酰胺、氧代吲哚及刺桐类生物碱合成中的应用研究（2页珍藏版）》请在金锄头文库上搜索。
1、氧化去芳化策略在-内酰胺、氧代吲哚及刺桐类生物碱合成中的应用研究摘要氧化去芳化反应可生成环己二烯酮这个非常重要且多官能团化的合成砌块，在天然产物的合成中有广泛的应用，是近年来合成化学研究的热点。本论文研究了利用氧化去芳化策略合成-内酰胺化合物、氧代吲哚化合物、刺桐碱骨架的新方法。 本论文共分为五章，第一章主要综述了氧化去芳化反应及其在天然产物合成中的应用，其次对其他去芳化方法：还原去芳化、重排去芳化、过渡金属参与的去芳化作了简要的介绍。第二章研究了氧化去芳化合成-内酰胺化合物的方法。双羰基位亚甲基捕获氧化去芳化过程中间体而生成螺环内酰胺化合物，这是有效的形成碳碳键的方法。生成的螺环内酰胺化合物
2、是很好的合成子，并具有较好的抗肿瘤活性。第三章研究了氧化去芳化合成氧代吲哚化合物的方法。酚化合物经氧化去芳化、Michael加成、芳构化得到氧代吲哚化合物，并获得了是合成天然产物Horsfiline及其类似物的关键中间体。第四章研究了氧化去芳化构建刺桐碱骨架的合成策略。酚化合物经氧化去芳化， Michael加成而构建了刺桐碱的四环骨架环系。再经氢化、脱酯基而完成了3-Demethoxyerythratidinone的形式合成。本章中还探索了不对称Michael加成去对称化反应，得到了65%的ee值。第五章为论文中相关化合物的合成实验操作及其谱图数据。关键词：氧化去芳化策略，螺环内酰胺，氧代吲哚
3、，刺桐碱ABSTRACT Cyclohexadienones produced by oxidative dearomatization are important and multifunctional building blocks, which have been used as intermediates in natural product synthesis. Many synthetic chemists have focused on the field in recent years. This thesis describes a new approach towards
4、the synthesis of -lactam、oxyindole and the skeleton of Erythrina Alkaloids using the oxidative dearomatization strategy.This thesis have five chapters. In the first chapter, recent progress of oxidative dearomatization reactions and its applications in natural product synthesis is summarized. Other
5、methods for dearomatization are also briefly introduced , including reductive dearomatization、dearomatization by rearrangement and transition-metal- mediated dearomatization.In the second chapter, a new approach towards the synthesis of -lactam is studied. The intermediate of oxidative dearomatizati
6、on is captured by the activated methylene, and -lactam was obtained by C-C bonding formation. The spiro -lactams are good building blocks, and possess good anti-tumor activity against a number of tumor cell lines . In the third chapter, a new approach towards the synthesis of oxyindole is studied. T
7、he phenol compound is oxidized with IBD in the presence of MeOH. And the resulting ketones undergo Michael addition in the presence of DBU and rearomatization in the presence of acid produced oxyindoles. A key intermediate for the synthesis of Horsfiline was obtained .In the fourth chapter, the skel
8、eton of Erythrina Alkaloids is constructed using a dearomatization strategy. The intermediate of dearomatization is captured by an active aromatic ring and Michael addition of the spiro cyclohexadienone is produced tetracyclic framework of Erythrina Alkaloids. After hydrogenation and removal of the
9、ester, A formal synthesis of Erythrina Alkaloids, 3-Demethoxyerythratidinone, is completed. Asymmetry Michael addition towards to cyclohexadienone is also explored .In the fifth chapter, experimental data and procedures for all compounds is presented .Key words: dearomatization, spiro -lactam, oxyindole, Erythrina Alkaloids
