重氮化合物参与的化学催化反应研究
发布时间：2018-07-14 12:01
【摘要】：本篇论文主要包括两部分的研究:在第一部分主要研究基于捕捉两性离子中间体的多组分反应研究以及吲哚与重氮化合物的不对称C-H官能团化反应;第二部分主要研究过渡金属催化的丙炔基重氮乙酸酯的化学反应。多组分反应可以在一步反应中高效构建多个化学键而受到广泛的关注。因此,发现新的多组分反应当代有机合成化学有很高需求。另外,发展不对称的多组分反应不仅具有很高的挑战性而且还可以为更进一步的理解已报道的反应。在我们课题组在通过捕捉活泼中间体领域取得了成果的基础上,我们预测由吲哚与金属卡宾化合物产生的两性离子可以被一些亲电试剂所捕捉。在我们课题组已经报道了醋酸铑与手性磷酸不对称共催化多组分反应基础上,我们利用这种方法成功地实现了吲哚,重氮化合物和亚胺的多组分反应,该反应可用于合成多官能团化取代的吲哚化合物衍生物。为了进一步理解两性离子的质子传递过程,我们设计了一个氘代实验:结果在这个反应中发现了"非直接的质子传递过程",这个发现为我们提供了一种通过手性质子梭实现不对称C-H官能团化的设计思路。多样性合成为大量合成结构复杂多样的小分子提供了一种非常高效的策略。在2003年,Stuart L.Schreiber与其合作者提出了两种基本的方法:基于底物的合成方法和基于试剂的合成方法,这两种策略在多样性合成领域取得了很大的成功。然而,基于催化剂的化学多样性合成长期以来并没有得到足够的重视。针对我们课题组在卡宾领域的兴趣,我们提出了如果同时有两个卡宾的前体,哪一个会优先反应呢?为了回答这个问题,我们合成了丙炔基重氮乙酸酯,一个具有重氮基团与炔基的的化合物,这两种基团都可以形成金属卡宾中间体。我们研究了不同金属对这个化合物的反应。发现了 1)铑、钯、银、铜等金属可以催化卡宾/炔烃复分解串联反应;2)金显示出非常特殊的化学性质,可以选择性的活化三键而保留重氮基团的氮原子。在我们研究一系列金催化的反应中,我们发现加入当量的4-氯氧化吡啶使丙炔基重氮乙酸酯发生重排得到(Z)-1,3-双烯-重氮化合物和重氮-双烯-[4+2]环加成产物。并且发现(Z)-1,3-双烯-重氮化合物不可以发生这个分子内环加成反应。接下来我们对这个重氮-双烯-[4+2]环加成反应进行了动力学研究得到了这个反应的活化能,熵变以及焓变等数据。另外,我们还研究了这个反应的Hammett方程。串联反应是在一步反应中发生一系列连续的化学转化,可以一步反应构建结构复杂的化合物,具有高效,节约资源、时间、成本等优点。由于这些优点,发展新型的串联反应是现代有机合成的重要部分。具有多官能团的底物被认为是反应发生的基础。我们受金催化的丙炔酸酯与不饱和亚胺的[4+3]-环加成反应的启发,我们用重氮修饰之后的丙炔酸酯与不饱和亚胺反应,希望可以得到重氮修饰之后的[4+3]-环加成反应产物。意料之外的是,我们得到了一个二酮的产物。通过核磁监控反应,在反应开始前5分钟,我们发现[4+3]-环加成中间体。经过不懈努力,我们分离了纯的[4+3]-环加成中间体,并且在发现[4+3]-环加成中间体不用催化剂的作用下即可重排到二酮产物。与此对照的是,加入5 mol%的金催化剂只给出微量的二酮产物,说明这个过程是一个非金属参与的过程。
[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.
【学位授予单位】：华东师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：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.
【学位授予单位】：华东师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.251
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