多个Akuammiline类吲哚生物碱的不对称合成研究

发布时间：2018-03-17 00:12

本文选题：吲哚生物碱　切入点：(-)-Aspidophylline　出处：《兰州大学》2017年博士论文　论文类型：学位论文

【摘要】：本论文分为三章:(1)Akuammiline类生物碱的合成进展,(2)Aspidophylline A的不对称全合成研究,(3)与Aspidophylline A相关的Akuammiline类生物碱的不对称合成研究。第一章:Akuammiline类生物碱的合成进展简单地介绍了Akuammiline类生物碱的背景,包括这类生物碱的分离,结构特征,生理活性以及可能生源合成途径。同时本章也简略地总结了Vincorine,Aspidophylline A,Picrinine,Scholarisine A以及Strictamine的合成进展。第二章:Aspidophylline A的不对称全合成研究Aspidophylline A是一个复杂的五环Akuammiline类生物碱,其结构特征为:包含一个吲哚并呋喃结构;一个氮杂[3,3,1]的桥环;五个连续的手性中心,其中一个为全碳季碳,五个手性中心都来自于同一个多取代的六元环。通过分子内的串联金催化环化反应和钯催化的甲氧羰基化反应,实现了富有挑战性的(±)-Aspidophylline A四环骨架的构筑,最终完成了(±)-Aspidophylline A的形式合成。同时也实现了(-)-Aspidophylline A的不对称合成。关键反应包括:1)铑催化的不对称还原炔酮反应,引入了第一个手性中心,通过底物的诱导,控制(-)-Aspidophylline A中其它手性中心;2)金催化炔基吲哚和亚胺的6-exo-dig环化反应,构筑了天然产物中的一个全碳季碳;3)立体选择性的分子内的氧化叠氮烷氧化反应。第三章:与Aspidophylline A相关的Akuammiline类生物碱的不对称合成研究。本章利用串联金催化环化策略,展开了其它几个与Aspidophylline A相关的Akuammiline类生物碱的合成研究,并取得了一定进展,相关的研究正在进行中。
[Abstract]:This thesis is divided into three chapters: the progress in the synthesis of Akuammiline alkaloids and the asymmetric total synthesis of Aspidophylline A) the asymmetric synthesis of Akuammiline alkaloids related to Aspidophylline A. the first chapter introduces the background of the synthesis of Akuammiline alkaloids. Including the separation and structural characteristics of these alkaloids, This chapter also briefly summarizes the progress in the synthesis of Aspidophylline A and Strictamine. Chapter 2: the asymmetric synthesis of Aspidophylline A is a complex pentacyclic Akuammiline alkaloid. Its structural characteristics are as follows: an indole furan structure; a bridged ring of azo [3]; and five consecutive chiral centers, one of which is a total carbon quaternary carbon, The five chiral centers are all derived from the same polysubstituted six-member ring. Through intramolecular gold catalyzed cyclization and palladium catalyzed methoxycarbonylation, a challenging (卤Aspidophylline A) four-ring framework was constructed. At the same time, the asymmetric synthesis of Aspidophylline A was also realized. The key reactions included the rhodium catalyzed asymmetric reduction of acetylene ketones, and the introduction of the first chiral center, which was induced by the substrate. Gold was used to catalyze 6-exo-dig cyclization of indoles and imines in Aspidophylline A. A total carbon quaternary carbon 3) stereoselective intramolecular oxidation of azide was constructed. Chapter 3: asymmetric synthesis of Akuammiline alkaloids associated with Aspidophylline A. in this chapter, series gold catalyzed cyclization strategy is used. Several other Akuammiline alkaloids related to Aspidophylline A have been studied, and some progress has been made.
【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O629.3

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