內(nèi)半縮醛在有機催化不對稱反應中的應用
發(fā)布時間：2018-08-13 13:34
【摘要】：有機催化的不對稱合成從2000開始引起了世界各地的科學家們廣泛的關(guān)注,并收獲了豐碩的科研成果。從新型催化劑的研發(fā),復雜反應機理的探索和證明,到新奇路線的巧妙設(shè)計和多手性中心骨架的構(gòu)建以及最后的工業(yè)化運用,使得有機催化在不對稱領(lǐng)域占有了重要的位置。因此,發(fā)展新的適用于有機催化的底物并得到一些特定的骨架具有重要的意義。本論文主要圍繞一個全新的有機催化底物—內(nèi)半縮醛,展開-系列的研究。氫化香豆素骨架廣泛的存在于活性天然產(chǎn)物中,由廉價易得的香豆素出發(fā),不對稱修飾氫化香豆素骨架具有重要意義。論文的第一部分提出了一個全新的“開-關(guān)”策略。首先,還原氫化香豆素中的內(nèi)酯為內(nèi)半縮醛完成“開”的步驟,再以手性仲胺為催化劑,催化內(nèi)半縮醛和缺電子的烯烴發(fā)生不對稱的Michael反應,最后氧化內(nèi)半縮醛為內(nèi)酯完成“關(guān)”的步驟。該反應具有產(chǎn)率高和立體選擇性好(大部分ee＞99%),容易操作,環(huán)境友好等優(yōu)點。最終的產(chǎn)物可以通過一系列的衍生獲得了多種不同骨架的具有光學活性的化合物。值得注意的是,這是首次把內(nèi)半縮醛運用在有機催化的不對稱合成中,為未來該領(lǐng)域的研究開辟了一條新的道路。螺環(huán)氧化吲哚骨架由于其優(yōu)秀的生理學和藥學活性一直以來都是不對稱合成中的熱點。尤其是螺環(huán)為全手性中心的六元碳環(huán)化合物的合成備受化學家們的關(guān)注。論文的第二部分報道了一個使用不對稱[2+2+2]串聯(lián)策略,通過有機/有機雙催化體系構(gòu)建六元碳環(huán)化合物。該產(chǎn)物包括六個連續(xù)的手性中心,而且其中一個手性中心為季碳,同時還包含螺環(huán)氧化吲哚骨架部分。于此同時,該反應是繼內(nèi)半縮醛運用在有機催化的不對稱合成中的又一個新的拓展。
[Abstract]:The asymmetric synthesis of organic catalysis has attracted the attention of scientists all over the world since 2000, and has yielded fruitful results. From the research and development of new catalyst, the exploration and proof of complex reaction mechanism, the ingenious design of novel route, the construction of multi-chiral center skeleton and the final industrial application, organic catalysis occupies an important position in the field of asymmetry. Therefore, it is of great significance to develop new substrates suitable for organic catalysis and obtain some specific skeletons. This paper focuses on a new organic catalytic substrate-internal semi-acetal, starting-series of research. Hydrocoumarin skeleton widely exists in active natural products. It is of great significance to modify the hydrocoumarin skeleton asymmetrically from the cheap and easily available coumarin skeleton. In the first part of this paper, a new strategy of "on-off" is put forward. First, the lactone in the hydrogenated coumarin was used as the inner hemiacetal to complete the "opening" step, and then the asymmetric Michael reaction between the inner hemiacetal and the electron-deficient olefins was catalyzed with chiral secondary amine as the catalyst. The final oxidation of the inner half acetal for lactone to complete the "pass" step. This reaction has the advantages of high yield, good stereoselectivity (most ee > 99%), easy operation and environmental friendliness. The final product can be derived by a series of derivatives to obtain a variety of different skeletons with optical active compounds. It is worth noting that this is the first time that inner hemiacetal has been used in organic catalyzed asymmetric synthesis, which opens a new way for future research in this field. The spirocyclic indole skeleton has been a hot spot in asymmetric synthesis due to its excellent physiological and pharmaceutical activity. In particular, the synthesis of hexagonal carbon compounds with snail ring as a full chiral center has attracted much attention of chemists. In the second part of this paper, an asymmetric [222] tandem strategy is used to construct hexagonal carbocyclic compounds by organic / organic double catalysis system. The product consists of six consecutive chiral centers, one of which is quaternary carbon, and also contains the spirocyclic indole skeleton. At the same time, the reaction is a new extension of the application of inner hemiacetal in organic catalyzed asymmetric synthesis.
【學位授予單位】：西南交通大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O621.251
本文編號：2181149
[Abstract]:The asymmetric synthesis of organic catalysis has attracted the attention of scientists all over the world since 2000, and has yielded fruitful results. From the research and development of new catalyst, the exploration and proof of complex reaction mechanism, the ingenious design of novel route, the construction of multi-chiral center skeleton and the final industrial application, organic catalysis occupies an important position in the field of asymmetry. Therefore, it is of great significance to develop new substrates suitable for organic catalysis and obtain some specific skeletons. This paper focuses on a new organic catalytic substrate-internal semi-acetal, starting-series of research. Hydrocoumarin skeleton widely exists in active natural products. It is of great significance to modify the hydrocoumarin skeleton asymmetrically from the cheap and easily available coumarin skeleton. In the first part of this paper, a new strategy of "on-off" is put forward. First, the lactone in the hydrogenated coumarin was used as the inner hemiacetal to complete the "opening" step, and then the asymmetric Michael reaction between the inner hemiacetal and the electron-deficient olefins was catalyzed with chiral secondary amine as the catalyst. The final oxidation of the inner half acetal for lactone to complete the "pass" step. This reaction has the advantages of high yield, good stereoselectivity (most ee > 99%), easy operation and environmental friendliness. The final product can be derived by a series of derivatives to obtain a variety of different skeletons with optical active compounds. It is worth noting that this is the first time that inner hemiacetal has been used in organic catalyzed asymmetric synthesis, which opens a new way for future research in this field. The spirocyclic indole skeleton has been a hot spot in asymmetric synthesis due to its excellent physiological and pharmaceutical activity. In particular, the synthesis of hexagonal carbon compounds with snail ring as a full chiral center has attracted much attention of chemists. In the second part of this paper, an asymmetric [222] tandem strategy is used to construct hexagonal carbocyclic compounds by organic / organic double catalysis system. The product consists of six consecutive chiral centers, one of which is quaternary carbon, and also contains the spirocyclic indole skeleton. At the same time, the reaction is a new extension of the application of inner hemiacetal in organic catalyzed asymmetric synthesis.
【學位授予單位】：西南交通大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O621.251
【相似文獻】
相關(guān)碩士學位論文 前2條
1 李志龍;內(nèi)半縮醛在有機催化不對稱反應中的應用[D];西南交通大學;2016年
2 曾靜;光學活性丁內(nèi)半縮醛的合成及在天然生物堿合成中的應用[D];廈門大學;2007年
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