兰州大学机构库 >化学化工学院
(+)-Iresin和 (+)-Aphidicolin的全合成
其他题名Total Synthesis of (+)-Iresin and (+)-Aphidicolin
王边琳
导师李卫东
学位类别博士
2014-05-30
关键词(+)-Aphidicolin (+)-Iresin 全合成 仿生多烯环化 高碘代烯丙基硅烷
中文摘要本论文以倍半萜内酯天然产物(+)-Iresin和四环二萜天然产物 (+)-Aphidicolin 的不对称全合成为研究目标,包括以下三个章节: 第一章概述了烯丙基硅的结构、化学反应性及制备方法,综述了其在以仿生多烯环化为关键反应的天然产物全合成中的应用,简要介绍了本研究小组发展的多官能团化高碘代烯丙基硅的合成方法及其在天然产物全合成中的应用研究。 第二章简要介绍了ent-Drimane 骨架天然产物 (+)-Iresin 的结构及其同系物的合成研究;详细描述了以本小组以往全合成穿心莲内酯的中间体醛 1-116 为重要前体化合物,经过酸氧化中间体 2-32 的 (+)-Iresin 的首次不对称全合成。 第三章介绍了四环二萜天然产物 (+)-Aphidicolin 的结构、生物活性、生源合成路径,以及(+)-Aphidicolin 的全合成策略,并对合成方法做了简要归类对比。进而详细描述了运用本小组发展的方法,由三个片段合成多官能团四取代高碘代烯丙基硅仿生环化前体3-130 及其在Lewis Acid条件下的环化反应,环化产物 3-136 和 3-137 分别经多步官能团转化合成了CoreyTius以及Holton 中间体,从而实现了(+)-Aphidicolin 的形式不对称全合成。本章还详细记录了异常分子内环丙烷化产物 3-167 的生成和结构表征。
英文摘要This thesis aims at the asymmetric total synthesis of sesquiterpene lactone (+)-Iresin and tetracyclic diterpenoid (+)-Aphidicolin and consists of the following three chapters: Chapter 1 summarized the structure, reactivity and synthetic methods of allylsianes, and their applications in natural product synthesis via biomimetic polyene cycizations. A brief introduction on the novel synthetic method of homoiodo allylsilanes previously developed in our research group was also given. Chapter 2 described the structure of the natural product (+)-Iresin which has a ent-Drimane skeleton and studies on the synthesis of the analogs of (+)-Iresin. We reported in detail the first asymmetric total synthesis of (+)-Iresin via the key oxidation intermediate 2-32 from the bicyclic aldehyde 1-116, Compound 1-116 was a key intermediate in our previous total synthesis of andrographolde. Chapter 3 described the structure, bioactivity, biomimmetic synthetic pathway and previously reported synthetic strategy for the tetracyclic diterpenoid (+)-Aphidicolin. A brief comparative account on the previous total synthetic methods was given. We employed three three components as building blocks for construction of the functionalized tetrasubstituted homoiodo allylsilane 3-130 based on our previous synthetic method, 3-130 was cyclized effectively under the action of Lewis acid to give tricyclic products 3-136 and 3-137. The asymmetric synthesis of the known CoreyTius intermediate was achieved via a series of functional group transformations from spiro-cyclic intermediates 3-136 or 3-137, thus constituting a formal total synthesis of (+)-Aphidicolin according to Holton’s previous synthesis (1987). The unusual formation of an intramolecular cyclopropanated ring system 3-167 was disclosed with full structural characterization.
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授予单位兰州大学
授予地点兰州
语种中文
文献类型学位论文
条目标识符http://ir.lzu.edu.cn/handle/262010/238704
Collection化学化工学院
Recommended Citation:
GB/T 7714
王边琳. (+)-Iresin和 (+)-Aphidicolin的全合成[D]. 兰州. 兰州大学,2014.
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