Paniculatine类型石松生物碱的合成研究
摘要
石松生物碱(Lycopodium alkaloids)是从蕨类植物石松及其近缘植物(Lycopodium related plants)中分离得到的结构相似,具有相同生源的一类天然生物碱。广泛存在于石松及其近缘植物中,石松类植物主要是石松科(Lycopodiaceae)和石杉科(Huperziaceae)的蕨类植物。石松生物碱由于结构多变且具有复杂的多环骨架和潜在的生物活性,为有机化学家提供了极具挑战的合成目标。Aldol反应是形成碳-碳键的有效方法之一,近年来一直是有机合成的研究热点。本论文主要描述以Aldol反应作为关键反应对Paniculatine类型石松生物碱展开的合成研究,共分为三章。
第一章重点介绍了Fawcettimine型石松生物碱的分类、生源推测、分离及合成研究进展,对Fawcettimine、Magellanin、Magellaninone和Paniculatine等分子的合成进行了综述。
第二章详细介绍了我们合成Paniculatine类型石松生物碱的策略以及过程中遇到的问题。按最初的逆合成分析进行Aldol反应来构筑B/C/D环,但是在构筑C环时Aldol反应没能发生,推测可能是位阻的原因和B环上羰基的影响。于是我们设计了第二代路线,以R-(+)-长叶香茅酮为起始原料,通过8步反应构建C/D环。
第三章为论文中相关化合物合成的实验操作及其谱图数据
Lycopodium alkaloids were isolated from the pteridophyta lycopodium and related plants with similar biogenesis. These compounds are present in lycopodium and related species, especially plants of Huperziaceae and Lycopodiaceae. The Lycopodium alkaloids often possess unusual skeletons and promising bioactivity, thus providing challenging targets to synthetic chemists. Direct Aldol reaction is one of the most powerful methods for formation of the carbon-carbon bond. It has attracted much attention in organic synthesis. In this thesis, Aldol reaction, as a key strategy, was used in the synthetic studies on the Paniculatine-type Lycopodium Alkaloids. Three chapters are included in this thesis.
In chapter1, We summarized the classification, biosynthesis, biological activities and syntheses of some well-known lycopodium alkaloids, which include Fawcettimine, Magellanine, Magellaninone and Paniculatine.
In chapter2, Our strategy analysis including the problems encountered in the course of the synthesis of the target molecules was discussed in details. Two different routes to construction of the tricyclic systems of the Paniculatine-type alkaloids were envisioned, and some key intermediates have been prepared in efficient manner from Pulegone.
In chapter3, The experimental procedure and spectum data of intermediate were recorded.
第一章重点介绍了Fawcettimine型石松生物碱的分类、生源推测、分离及合成研究进展,对Fawcettimine、Magellanin、Magellaninone和Paniculatine等分子的合成进行了综述。
第二章详细介绍了我们合成Paniculatine类型石松生物碱的策略以及过程中遇到的问题。按最初的逆合成分析进行Aldol反应来构筑B/C/D环,但是在构筑C环时Aldol反应没能发生,推测可能是位阻的原因和B环上羰基的影响。于是我们设计了第二代路线,以R-(+)-长叶香茅酮为起始原料,通过8步反应构建C/D环。
第三章为论文中相关化合物合成的实验操作及其谱图数据
Lycopodium alkaloids were isolated from the pteridophyta lycopodium and related plants with similar biogenesis. These compounds are present in lycopodium and related species, especially plants of Huperziaceae and Lycopodiaceae. The Lycopodium alkaloids often possess unusual skeletons and promising bioactivity, thus providing challenging targets to synthetic chemists. Direct Aldol reaction is one of the most powerful methods for formation of the carbon-carbon bond. It has attracted much attention in organic synthesis. In this thesis, Aldol reaction, as a key strategy, was used in the synthetic studies on the Paniculatine-type Lycopodium Alkaloids. Three chapters are included in this thesis.
In chapter1, We summarized the classification, biosynthesis, biological activities and syntheses of some well-known lycopodium alkaloids, which include Fawcettimine, Magellanine, Magellaninone and Paniculatine.
In chapter2, Our strategy analysis including the problems encountered in the course of the synthesis of the target molecules was discussed in details. Two different routes to construction of the tricyclic systems of the Paniculatine-type alkaloids were envisioned, and some key intermediates have been prepared in efficient manner from Pulegone.
In chapter3, The experimental procedure and spectum data of intermediate were recorded.
引文
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