Gastrodinol和(±)-Oberonin A及其异构体的全合成研究

	Gastrodinol和(±)-Oberonin A及其异构体的全合成研究; Studies on the Total Synthesis of Gastrodinol、 (±)-Oberonin A and Its Isomers
	吕永峰
导师	周俊
摘要	This thesis is mainly composed of three parts: (1) The application of 6π electrocyclization in the total synthesis of natural products; (2) Studies on the total synthesis of Gastrodinol; (3) Studies on the total synthesis of (±)-Oberonin A and its isomers. In chapter 1, we summarize the application examples of 6π electrocyclization and 6π electrocyclization/aromatization synthetic strategies in the total synthesis of natural products. In chapter 2, we describe studies on the total synthesis of Gastrodinol. By analyzing the structural characteristics of the target molecule, we chose 6π electrocyclization reaction as the key step in the synthesis of the target molecule to construct the B ring. On this basis, we explored a more efficient synthetic route. Using phloroglucinol 2-14 and 1,3-cyclopentadione 2-8 as starting materials, the key intermediates 2-13 and 2-6 were obtained via 10 steps and 4 steps, respectively. With the key intermediates in hand, utilizing the convergent synthesis strategy, we smoothly furnish compound 2-12 via Sonogashira coupling reaction between intermediates 2-13 and 2-6. Then compound 2-10 was successfully prepared from compound 2-12 through Lindlar reduction and photocatalytic 6π electrocyclization (isomerization, electrocyclization, aromatization) reaction, and finally we obtained the target natural product after removing the benzyl group. The first total synthesis of gastrodinol was achieved in the longest linear 14 steps with an overall yield of 3.9 %, which has provided sufficient material guarantee for later pharmacological experiment. In chapter 3, we describe studies on the total synthesis of (±)-Oberonin A and its isomers. By analyzing the structural characteristics of the target molecule, we chose the Diels-Alder reaction as the key step in the synthesis of the target molecule to construct the B ring. On this basis, we explored a more efficient synthetic route. Using commercially available vanillin 3-6 as the starting material, the diene 3-14 was obtained through bromination, selective methylation, Suzuki coupling reaction. And the dienophile 3-7 was obtained through nucleophilic addition and IBX oxidation. With the key intermediates in hand, Diels-Alder reaction was occurred between the diene 3-14 and the dienophile 3-7, finally yielded DA reaction products with two configurations (endo and exo). Then the DA products of the two configurations were subjected to LiAlH4 reduction, selective methylation, DMP and Pinnick oxidation, esterification reaction to furnish (±)-Oberonin A and the other three isomers (all are enantiomers). The first total synthesis of (±)-Oberonin A and the other three isomers (all are enantiomers) were achieved in the longest linear 16 steps, which has provided sufficient material guarantee for later pharmacological experiment.
	2020-11
文献类型	学位论文
条目标识符	http://ir.kib.ac.cn/handle/151853/74240
专题	昆明植物所硕博研究生毕业学位论文
推荐引用方式 GB/T 7714	吕永峰. Gastrodinol和(±)-Oberonin A及其异构体的全合成研究, Studies on the Total Synthesis of Gastrodinol、 (±)-Oberonin A and Its Isomers[D],2020.

条目包含的文件
文件名称/大小	文献类型	版本类型	开放类型	使用许可
吕永峰-博士学位论文-吕永峰6fa69b（8632KB）	学位论文		限制开放	CC BY-NC-SA	请求全文