若干生物碱全合成及铱催化不对称烯丙基-烯丙基交叉偶联反应研究

	若干生物碱全合成及铱催化不对称烯丙基-烯丙基交叉偶联反应研究; Total Syntheses of Several Alkaloids and Ir-Catalyzed Enantioselective Allyl‐Allyl Cross-Coupling
	郑瑜
导师	杨玉荣
摘要	The dissertation mainly covers the total synthesis of seven alkaloids and one methodology of Ir-catalyzed asymmetric allylation, including the following chapters (1) asymmetric total synthesis of tetrahydro-β-carboline alkaloid (?)-geissoschizol; (2) asymmetric total syntheses of tetrahydroisoquinoline alkaloids (?)-fennebricin A, (?)-renieramycin J, (?)-renieramycin G, (?)-renieramycin M, and (?)-jorunnamycin A; (3) first total synthesis of monoterpenoid indole alkaloid (?)-arbornamine; and (4) iridium-catalyzed enantioselective allyl-allylboronate cross-coupling. In chapter 1, asymmetric total synthesis of tetrahydro-β-carboline alkaloid (?)-geissoschizol through Ir-catalyzed allylic amidation was outlined. Tetrahydro-β-carboline alkaloids are a large class of natural products with unique structures and extensive biological activities. In this study, an alternative strategy, in which a highly enantioselective (>99% ee), intramolecular Ir-catalyzed allylic amidation of a secondary alcohol derived from tryptamine was utilized to replace the traditional asymmetric reduction or asymmetric Pictet-Spengler reactions, was tactically utilized to forge chiral tetrahydro-β-carboline skeleton. Based on this key step, a novel, facile, enantioselective total synthesis of (?)-geissoschizol was achieved in 10 steps. In chapter 2, collective total synthesis of five tetrahydroisoquinoline alkaloids including the first total synthesis of (?)-fennebricin A and (?)-renieramycin J was outlined. The tetrahydroisoquinoline antibiotics have been studied thoroughly over the past four decades due to the intriguing chemical structures, potent antitumor and antimicrobial activities, and unique mechanisms. In this study, first asymmetric total synthesis of (?)-fennebricin A and (?)-renieramycin J was achieved in a longest linear sequence of 20 steps from 2,6-dimethoxy-toluene with an overall yield of 4% and 3%, respectively. Renieramycin G, jorunnamycin A, and renieramycin M have also been synthesized using same strategies. The synthesis features symmetrically constructing the pentacycle of tetrahydroisoquinoline alkaloids from a single common amino acid that was readily prepared with the Yu’s palladium-catalyzed arylation of alanine-derived amide. In addition, the structure of (?)-renieramycin M has been confirmed by single crystal X-ray analysis for the first time. In chapter 3, first total synthesis of monoterpenoid indole alkaloid (?)-arbornamine was outlined. Arbornamine is a novel monoterpene indole alkaloid isolated in 2016 by Kam and co-workers from a Malayan Kopsia arborea, possessing a unique 6/5/6/5/6 “arbornane” skeleton. In this study, a concise total synthesis of (?)-arbornamine has been achieved in 6 steps and 31% overall yield from three readily available known compounds. The synthesis features a cascade involving a Pictet-Spengler cyclization/intramolecular ammonolysis to create the “arbornane” tetracyclic core in a single chemical operation. The subsequen
	2020-05
文献类型	学位论文
条目标识符	http://ir.kib.ac.cn/handle/151853/74224
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	郑瑜. 若干生物碱全合成及铱催化不对称烯丙基-烯丙基交叉偶联反应研究, Total Syntheses of Several Alkaloids and Ir-Catalyzed Enantioselective Allyl‐Allyl Cross-Coupling[D],2020.

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