一种新型苯并二氢呋喃类木脂素的合成研究

发布时间：2018-04-24 09:47

本文选题：苯并二氢呋喃类木脂素 + 全合成　；参考：《青岛科技大学》2014年硕士论文

【摘要】：木脂素类化合物是一类由苯丙素单元氧化聚合形成的天然产物，在自然界中分布较为广泛，具有独特的药理活性。由于其具有新颖的化学结构、多个手性中心、以及丰富的官能团使其成为了化学家们广泛关注的焦点。其中本文关注的苯并二氢呋喃类木脂素以及8-5’新木脂素也是具有广泛生理和药理活性的天然木脂素。本文主要对苯并二氢呋喃类新木脂素Boehmenan H进行了首次全合成研究，并对8-5’新木脂素的合成进行了探索，本文内容共包括以下三部分：第一部分综述，介绍了木脂素化合物目前研究现状包括其分类、理化性质及其生物活性等等。主要阐述了天然木脂素类化合物的合成研究，并根据当前的研究现状提出本课题的主要内容及研究方向。第二部分详细介绍了苯并二氢呋喃类木脂素Boehmenan H的首次全合成研究。以廉价的香草醛为原料，与丙二酸二乙酯经过克脑文盖反应生成阿魏酸乙酯，通过氧化银催化的仿生氧化偶联反应，形成了苯并二氢呋喃骨架。通过两次酯基的还原和一次羟基的DHP保护，得到中间产物单醇，最后和甲氧基甲醚保护的阿魏酸衍生物反应，得到前目标化合物，然后再经过脱除保护基得到具有药理活性的目标化合物Boehmenan H。第三部分主要介绍了苯并二氢呋喃环在不同的碱性条件下的开环反应，并深入探讨了它们的开环反应机理。这些开环反应证明了苯并二氢呋喃环在碱性条件下很不稳定，，极易开环，为8-5’新木脂素类化合物合成提供了新的方法和途径。
[Abstract]:Lignans are a kind of natural products formed by unit oxidation polymerization of phenylpropanin, which are widely distributed in nature and have unique pharmacological activities. Because of its novel chemical structure, many chiral centers and abundant functional groups, it has become the focus of chemists. The benzodihydrofuran lignans and 8-5 '-neophorin are also natural lignans with a wide range of physiological and pharmacological activities. In this paper, the first total synthesis of benzodihydrofuran new lignans (Boehmenan H) was studied, and the synthesis of 8-5 'new lignans was explored. In the first part, the present research status of lignans including their classification, physicochemical properties and biological activities were reviewed. In this paper, the synthesis of natural lignans is reviewed, and the main contents and research directions of this subject are put forward according to the current research situation. In the second part, the first total synthesis of benzodihydrofuran lignans (Boehmenan H) was introduced in detail. Using cheap vanillin as raw material, diethyl malonate was reacted with diethyl malonate to form ethyl ferulic acid, and the benzodihydrofuran skeleton was formed by the bionic oxidative coupling reaction catalyzed by silver oxide. Through the reduction of two ester groups and the DHP protection of the first hydroxyl group, the intermediate monoalcohol was obtained. Finally, the intermediate product was reacted with the ferulic acid derivative protected by methoxy methyl ether, and the former target compound was obtained. After removing the protective group, the target compound with pharmacological activity, Boehmenan H. In the third part, the ring opening reaction of benzodihydrofuran ring under different basic conditions was introduced, and the mechanism of ring opening reaction was discussed. These ring-opening reactions have proved that the benzodihydrofuran ring is unstable and easy to open in alkaline conditions, which provides a new method and approach for the synthesis of 8-5 '-lignans.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R914

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