本文選題：吲哚生物堿　切入點：(-)-Aspidophylline　出處：《蘭州大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：本論文分為三章:(1)Akuammiline類生物堿的合成進展,(2)Aspidophylline A的不對稱全合成研究,(3)與Aspidophylline A相關(guān)的Akuammiline類生物堿的不對稱合成研究。第一章:Akuammiline類生物堿的合成進展簡單地介紹了Akuammiline類生物堿的背景,包括這類生物堿的分離,結(jié)構(gòu)特征,生理活性以及可能生源合成途徑。同時本章也簡略地總結(jié)了Vincorine,Aspidophylline A,Picrinine,Scholarisine A以及Strictamine的合成進展。第二章:Aspidophylline A的不對稱全合成研究Aspidophylline A是一個復(fù)雜的五環(huán)Akuammiline類生物堿,其結(jié)構(gòu)特征為:包含一個吲哚并呋喃結(jié)構(gòu);一個氮雜[3,3,1]的橋環(huán);五個連續(xù)的手性中心,其中一個為全碳季碳,五個手性中心都來自于同一個多取代的六元環(huán)。通過分子內(nèi)的串聯(lián)金催化環(huán)化反應(yīng)和鈀催化的甲氧羰基化反應(yīng),實現(xiàn)了富有挑戰(zhàn)性的(±)-Aspidophylline A四環(huán)骨架的構(gòu)筑,最終完成了(±)-Aspidophylline A的形式合成。同時也實現(xiàn)了(-)-Aspidophylline A的不對稱合成。關(guān)鍵反應(yīng)包括:1)銠催化的不對稱還原炔酮反應(yīng),引入了第一個手性中心,通過底物的誘導(dǎo),控制(-)-Aspidophylline A中其它手性中心;2)金催化炔基吲哚和亞胺的6-exo-dig環(huán)化反應(yīng),構(gòu)筑了天然產(chǎn)物中的一個全碳季碳;3)立體選擇性的分子內(nèi)的氧化疊氮烷氧化反應(yīng)。第三章:與Aspidophylline A相關(guān)的Akuammiline類生物堿的不對稱合成研究。本章利用串聯(lián)金催化環(huán)化策略,展開了其它幾個與Aspidophylline A相關(guān)的Akuammiline類生物堿的合成研究,并取得了一定進展,相關(guān)的研究正在進行中。
[Abstract]:This thesis is divided into three chapters: the progress in the synthesis of Akuammiline alkaloids and the asymmetric total synthesis of Aspidophylline A) the asymmetric synthesis of Akuammiline alkaloids related to Aspidophylline A. the first chapter introduces the background of the synthesis of Akuammiline alkaloids. Including the separation and structural characteristics of these alkaloids, This chapter also briefly summarizes the progress in the synthesis of Aspidophylline A and Strictamine. Chapter 2: the asymmetric synthesis of Aspidophylline A is a complex pentacyclic Akuammiline alkaloid. Its structural characteristics are as follows: an indole furan structure; a bridged ring of azo [3]; and five consecutive chiral centers, one of which is a total carbon quaternary carbon, The five chiral centers are all derived from the same polysubstituted six-member ring. Through intramolecular gold catalyzed cyclization and palladium catalyzed methoxycarbonylation, a challenging (鹵Aspidophylline A) four-ring framework was constructed. At the same time, the asymmetric synthesis of Aspidophylline A was also realized. The key reactions included the rhodium catalyzed asymmetric reduction of acetylene ketones, and the introduction of the first chiral center, which was induced by the substrate. Gold was used to catalyze 6-exo-dig cyclization of indoles and imines in Aspidophylline A. A total carbon quaternary carbon 3) stereoselective intramolecular oxidation of azide was constructed. Chapter 3: asymmetric synthesis of Akuammiline alkaloids associated with Aspidophylline A. in this chapter, series gold catalyzed cyclization strategy is used. Several other Akuammiline alkaloids related to Aspidophylline A have been studied, and some progress has been made.
【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O629.3

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