重氮化合物參與的化學(xué)催化反應(yīng)研究
發(fā)布時間：2018-07-14 12:01
【摘要】：本篇論文主要包括兩部分的研究:在第一部分主要研究基于捕捉兩性離子中間體的多組分反應(yīng)研究以及吲哚與重氮化合物的不對稱C-H官能團化反應(yīng);第二部分主要研究過渡金屬催化的丙炔基重氮乙酸酯的化學(xué)反應(yīng)。多組分反應(yīng)可以在一步反應(yīng)中高效構(gòu)建多個化學(xué)鍵而受到廣泛的關(guān)注。因此,發(fā)現(xiàn)新的多組分反應(yīng)當(dāng)代有機合成化學(xué)有很高需求。另外,發(fā)展不對稱的多組分反應(yīng)不僅具有很高的挑戰(zhàn)性而且還可以為更進一步的理解已報道的反應(yīng)。在我們課題組在通過捕捉活潑中間體領(lǐng)域取得了成果的基礎(chǔ)上,我們預(yù)測由吲哚與金屬卡賓化合物產(chǎn)生的兩性離子可以被一些親電試劑所捕捉。在我們課題組已經(jīng)報道了醋酸銠與手性磷酸不對稱共催化多組分反應(yīng)基礎(chǔ)上,我們利用這種方法成功地實現(xiàn)了吲哚,重氮化合物和亞胺的多組分反應(yīng),該反應(yīng)可用于合成多官能團化取代的吲哚化合物衍生物。為了進一步理解兩性離子的質(zhì)子傳遞過程,我們設(shè)計了一個氘代實驗:結(jié)果在這個反應(yīng)中發(fā)現(xiàn)了"非直接的質(zhì)子傳遞過程",這個發(fā)現(xiàn)為我們提供了一種通過手性質(zhì)子梭實現(xiàn)不對稱C-H官能團化的設(shè)計思路。多樣性合成為大量合成結(jié)構(gòu)復(fù)雜多樣的小分子提供了一種非常高效的策略。在2003年,Stuart L.Schreiber與其合作者提出了兩種基本的方法:基于底物的合成方法和基于試劑的合成方法,這兩種策略在多樣性合成領(lǐng)域取得了很大的成功。然而,基于催化劑的化學(xué)多樣性合成長期以來并沒有得到足夠的重視。針對我們課題組在卡賓領(lǐng)域的興趣,我們提出了如果同時有兩個卡賓的前體,哪一個會優(yōu)先反應(yīng)呢?為了回答這個問題,我們合成了丙炔基重氮乙酸酯,一個具有重氮基團與炔基的的化合物,這兩種基團都可以形成金屬卡賓中間體。我們研究了不同金屬對這個化合物的反應(yīng)。發(fā)現(xiàn)了 1)銠、鈀、銀、銅等金屬可以催化卡賓/炔烴復(fù)分解串聯(lián)反應(yīng);2)金顯示出非常特殊的化學(xué)性質(zhì),可以選擇性的活化三鍵而保留重氮基團的氮原子。在我們研究一系列金催化的反應(yīng)中,我們發(fā)現(xiàn)加入當(dāng)量的4-氯氧化吡啶使丙炔基重氮乙酸酯發(fā)生重排得到(Z)-1,3-雙烯-重氮化合物和重氮-雙烯-[4+2]環(huán)加成產(chǎn)物。并且發(fā)現(xiàn)(Z)-1,3-雙烯-重氮化合物不可以發(fā)生這個分子內(nèi)環(huán)加成反應(yīng)。接下來我們對這個重氮-雙烯-[4+2]環(huán)加成反應(yīng)進行了動力學(xué)研究得到了這個反應(yīng)的活化能,熵變以及焓變等數(shù)據(jù)。另外,我們還研究了這個反應(yīng)的Hammett方程。串聯(lián)反應(yīng)是在一步反應(yīng)中發(fā)生一系列連續(xù)的化學(xué)轉(zhuǎn)化,可以一步反應(yīng)構(gòu)建結(jié)構(gòu)復(fù)雜的化合物,具有高效,節(jié)約資源、時間、成本等優(yōu)點。由于這些優(yōu)點,發(fā)展新型的串聯(lián)反應(yīng)是現(xiàn)代有機合成的重要部分。具有多官能團的底物被認(rèn)為是反應(yīng)發(fā)生的基礎(chǔ)。我們受金催化的丙炔酸酯與不飽和亞胺的[4+3]-環(huán)加成反應(yīng)的啟發(fā),我們用重氮修飾之后的丙炔酸酯與不飽和亞胺反應(yīng),希望可以得到重氮修飾之后的[4+3]-環(huán)加成反應(yīng)產(chǎn)物。意料之外的是,我們得到了一個二酮的產(chǎn)物。通過核磁監(jiān)控反應(yīng),在反應(yīng)開始前5分鐘,我們發(fā)現(xiàn)[4+3]-環(huán)加成中間體。經(jīng)過不懈努力,我們分離了純的[4+3]-環(huán)加成中間體,并且在發(fā)現(xiàn)[4+3]-環(huán)加成中間體不用催化劑的作用下即可重排到二酮產(chǎn)物。與此對照的是,加入5 mol%的金催化劑只給出微量的二酮產(chǎn)物,說明這個過程是一個非金屬參與的過程。
[Abstract]:This paper mainly includes two parts: in the first part, we mainly study the multi component reaction study based on the capture of amphoteric ion intermediates and the asymmetric C-H functionalization of indole and diazo compounds; the second part mainly studies the chemical reactions of the propargyl diazoacetate catalyzed by transition metals. It is widely paid attention to the efficient construction of multiple chemical bonds in one step reaction. Therefore, it is found that the new multi component reaction has high demand for contemporary organic synthesis chemistry. In addition, the development of asymmetric multi component reactions is not only very challenging but also can be reported for further reasons. On the basis of capturing the field of active intermediates, we predict that the amphoteric ions produced by indoles and metal CABBEEN compounds can be captured by some electrophilic reagents. In our group, we have reported the successful implementation of this method on the basis of the asymmetric co catalysis of rhodium acetate and chiral phosphoric acid. In order to further understand the proton transfer process of the amphoteric ions, we designed a deuterium generation experiment in order to further understand the proton transfer process of the amphoteric ions. In this reaction, we found the "non direct proton transfer process", which is the discovery for me. We provide a design idea for the implementation of asymmetric C-H functionalization through chiral proton shuttle. Diversity synthesis provides a very efficient strategy for a large number of small molecules with complex and diverse structures. In 2003, Stuart L.Schreiber and its co authors proposed two basic methods: substrate based synthesis and reagents based on the reagent. The two strategies have achieved great success in the field of diversity synthesis. However, the synthesis of chemical diversity based on the catalyst has not been paid enough attention for a long time. In view of our interest in the CABBEEN field, we have proposed that if there are two CABBEEN precursors at the same time, which one will give priority to the reaction? To answer this question, we have synthesized a propargyl diazoacetate, a compound with a diazo group and a alkynyl group. These two groups can form a metal CABBEEN intermediate. We have studied the reaction of different metals to this compound. We found that 1) rhodium, palladium, silver, copper and other metals can catalyze the complex decomposition of CABBEEN / alkynes in series. 2) gold shows a very special chemical property, which can selectively activate the three bonds and retain the nitrogen atom of the diazo group. In our study of a series of gold catalyzed reactions, we found that the equivalent 4- Chloropyridine was added to rearrange propropargyl diazoacetate to get (Z) -1,3- diene diazocompounds and diazotene -[4+2]. It was found that the (Z) -1,3- diene diazo compound did not have this intramolecular cycloaddition reaction. Next we studied the kinetics of the diazo diene -[4+2] ring addition reaction, and obtained the activation energy, entropy change and enthalpy change of this reaction. In addition, we also studied the Hammett side of this reaction. Series reaction is a series of continuous chemical conversion in one step reaction, which can one step to build complex compounds with high efficiency and save resources, time and cost. Because of these advantages, the development of new series reaction is an important part of modern organic synthesis. We are inspired by the reaction of the gold catalyzed proproparyne with the [4+3]- ring addition of the unsaturated imide. We use the propargate after the diazonium modification to react with the unsaturated imide. We hope to get the [4+3]- ring after the diazonium modification, and we are expected to get a product of two ketones. After the NMR monitoring, we found the [4+3]- ring addition intermediate 5 minutes before the start of the reaction. After unremitting efforts, we separated the pure [4+3]- cycloaddition intermediates, and we found that the [4+3]- ring addition intermediate could rearrange to the two ketone product without the catalyst. In contrast, the gold catalyst added to the 5 mol% was only given. A trace two ketone product indicates that this process is a non-metallic participation process.
【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O621.251
[Abstract]:This paper mainly includes two parts: in the first part, we mainly study the multi component reaction study based on the capture of amphoteric ion intermediates and the asymmetric C-H functionalization of indole and diazo compounds; the second part mainly studies the chemical reactions of the propargyl diazoacetate catalyzed by transition metals. It is widely paid attention to the efficient construction of multiple chemical bonds in one step reaction. Therefore, it is found that the new multi component reaction has high demand for contemporary organic synthesis chemistry. In addition, the development of asymmetric multi component reactions is not only very challenging but also can be reported for further reasons. On the basis of capturing the field of active intermediates, we predict that the amphoteric ions produced by indoles and metal CABBEEN compounds can be captured by some electrophilic reagents. In our group, we have reported the successful implementation of this method on the basis of the asymmetric co catalysis of rhodium acetate and chiral phosphoric acid. In order to further understand the proton transfer process of the amphoteric ions, we designed a deuterium generation experiment in order to further understand the proton transfer process of the amphoteric ions. In this reaction, we found the "non direct proton transfer process", which is the discovery for me. We provide a design idea for the implementation of asymmetric C-H functionalization through chiral proton shuttle. Diversity synthesis provides a very efficient strategy for a large number of small molecules with complex and diverse structures. In 2003, Stuart L.Schreiber and its co authors proposed two basic methods: substrate based synthesis and reagents based on the reagent. The two strategies have achieved great success in the field of diversity synthesis. However, the synthesis of chemical diversity based on the catalyst has not been paid enough attention for a long time. In view of our interest in the CABBEEN field, we have proposed that if there are two CABBEEN precursors at the same time, which one will give priority to the reaction? To answer this question, we have synthesized a propargyl diazoacetate, a compound with a diazo group and a alkynyl group. These two groups can form a metal CABBEEN intermediate. We have studied the reaction of different metals to this compound. We found that 1) rhodium, palladium, silver, copper and other metals can catalyze the complex decomposition of CABBEEN / alkynes in series. 2) gold shows a very special chemical property, which can selectively activate the three bonds and retain the nitrogen atom of the diazo group. In our study of a series of gold catalyzed reactions, we found that the equivalent 4- Chloropyridine was added to rearrange propropargyl diazoacetate to get (Z) -1,3- diene diazocompounds and diazotene -[4+2]. It was found that the (Z) -1,3- diene diazo compound did not have this intramolecular cycloaddition reaction. Next we studied the kinetics of the diazo diene -[4+2] ring addition reaction, and obtained the activation energy, entropy change and enthalpy change of this reaction. In addition, we also studied the Hammett side of this reaction. Series reaction is a series of continuous chemical conversion in one step reaction, which can one step to build complex compounds with high efficiency and save resources, time and cost. Because of these advantages, the development of new series reaction is an important part of modern organic synthesis. We are inspired by the reaction of the gold catalyzed proproparyne with the [4+3]- ring addition of the unsaturated imide. We use the propargate after the diazonium modification to react with the unsaturated imide. We hope to get the [4+3]- ring after the diazonium modification, and we are expected to get a product of two ketones. After the NMR monitoring, we found the [4+3]- ring addition intermediate 5 minutes before the start of the reaction. After unremitting efforts, we separated the pure [4+3]- cycloaddition intermediates, and we found that the [4+3]- ring addition intermediate could rearrange to the two ketone product without the catalyst. In contrast, the gold catalyst added to the 5 mol% was only given. A trace two ketone product indicates that this process is a non-metallic participation process.
【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O621.251
【相似文獻】
相關(guān)期刊論文 前10條
1 邵靖宇;;感光重氮化合物的應(yīng)用[J];化學(xué)世界;1952年01期
2 金關(guān)泰;Б.А.波采依考希茨;;談?wù)劮枷阕逯氐衔锏慕Y(jié)構(gòu)問題[J];化學(xué)通報;1960年02期
3 穆寶菡;;一種新的高速重氮感光劑——2,5-二乙氧基-4-(4＇-甲苯基硫代)苯重氮氯化鋅復(fù)鹽的合成[J];化學(xué)通報;1980年07期
4 ;染料增感重氮化合物的光解作用[J];感光材料;1978年03期
5 朱楚斌;許新華;章文迪;;重氮化合物屬性對曬圖紙性能的影響[J];天津造紙;1992年03期
6 袁翰青;;重氮化合物的發(fā)明人——格里斯[J];化學(xué)教育;1982年02期
7 董祥林;微泡法感光材料[J];感光材料;1975年04期
8 蔣媛;巧烤PS版[J];印刷技術(shù);1998年09期
9 嚴(yán)國兵;匡春香;彭程;王劍波;;鈀催化重氮化合物反應(yīng)的研究進展[J];有機化學(xué);2009年06期
10 王雪良;周，
本文編號：2121585
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2121585.html
最近更新
教材專著
