基于光致氧化还原和过渡金属催化的烯烃官能化反应的研究
发布时间：2019-02-08 17:45
【摘要】：烯烃的官能化反应是有机合成化学中最为基本的一种转化方式,是形成新化学键最为简单有效的方法,为构建多种多样的化合物骨架提供了丰富的碳源,该领域一直是化学家研究的热点。随着化学工业生产中造成的环境污染和能源危机问题越来越严重,使得探索反应条件更为温和(理想反应条件室温)、能源更为节约、对环境更为友好的反应体系去实现烯烃的官能化以及开发可持续发展、天然丰度大、环境友好的过渡金属催化剂进行烯烃官能化反应成为必然趋势。本论文的研究内容主要就是基于此背景确定的选题,分两章四小节介绍了利用这些策略发展起来的烯烃官能化反应的研究,具体内容如下:1.发展了在可见光促进下一步反应选择性生成C-N/C-C键用以合成多官能化二氢吡咯衍生物的方法。该反应操作简便、反应条件温和、底物适用性广。值得一提的是,该反应可以很容易地放大到克级规模,具有很强的实用性。应用此方法可以通过简单的一步反应得到多官能化的二氢吡咯核心骨架。2.基于该策略,同时发展了一种可见光促进生成亚胺自由基中间体,通过分子内环化非活化烯烃再分两种不同的途径分别得到氢亚胺化产物和氧亚胺化产物的方法。该策略主要在于通过构建C-N键高效合成3,4-二氢吡咯衍生物。该反应体系底物范围广,并都能以较好到优异的产率得到目标产物。3.发展了过渡金属铜催化环化非活化烯烃制备顺式-2,5-二取代吡咯烷类衍生物的方法。利用该方法制备的顺式产物可以进一步衍生化,为合成含顺式-2,5-二取代吡咯结构的药物分子或者天然产物提供一种有效的途径。4.最后,我们发展了过渡金属锰催化下通过C-H键活化、C-F键断裂途径的偕二氟烯烃的芳基化反应。本次报道的方法制备的E式产物作为主产物可以从E/Z混合产物中分离出来,通过C-H键活化合成E式单氟烯烃是首次报道。我们本次发展的策略补充了过渡金属锰催化体系的反应类型的同时也为制备氟化烯烃提供了一种可替代的方法。
[Abstract]:The functionalization of olefin is the most basic conversion method in organic synthesis chemistry. It is the simplest and most effective method to form new chemical bonds. It provides abundant carbon sources for the construction of a variety of compounds. This field has always been a hot topic for chemists. As the environmental pollution and energy crisis caused by the chemical industry become more and more serious, the exploration of reaction conditions is more mild (ideal reaction conditions at room temperature), and energy is more economical. In order to realize the functionalization of olefin and develop the sustainable development, it is an inevitable trend for the environmental friendly transition metal catalyst to realize the functionalization of olefin with large natural abundance and environmental friendly transition metal catalyst. The research content of this thesis is mainly based on this background. It is divided into two chapters and four sections to introduce the research of olefin functionalization reaction developed by these strategies. The specific contents are as follows: 1. A method for the synthesis of multifunctional dihydropyrrole derivatives by selective formation of C-N/C-C bond in the next step of reaction promoted by visible light has been developed. The reaction is easy to operate, the reaction conditions are mild, and the substrate is widely applicable. It is worth mentioning that the reaction can easily be scaled up to the gram scale, with strong practicality. Using this method, the multifunctional dihydropyrrole core skeleton can be obtained by a simple one-step reaction. Based on this strategy, a visible light to promote the formation of imine radical intermediates was developed. The hydroimide products and the oxyimide products were obtained by intramolecular cyclization of non-activated olefin in two different ways. The strategy is to efficiently synthesize 3'4-dihydropyrrole derivatives by constructing C-N bond. The reaction system has a wide range of substrates, and can obtain the target product by better yield. A method for the preparation of cis-2n-5-disubstituted pyrrolidine derivatives with transition metal copper catalyzed cyclization of non-active olefin was developed. The cis products prepared by this method can be further derivatized, which provides an effective way for the synthesis of drug molecules or natural products containing cis-2n 5-disubstituted pyrrole structure. 4. Finally, we developed the arylation of difluorinated olefins catalyzed by transition metal manganese through C-H bond activation and C-F bond breaking. The E-type products prepared by this method can be separated from the E / Z mixed products as the main products. The synthesis of E-type monofluoroolefins by C-H bond activation is reported for the first time. Our strategy not only complements the reaction type of transition metal manganese catalyst system, but also provides an alternative method for the preparation of fluorinated olefins.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.251
，
本文编号：2418639
[Abstract]:The functionalization of olefin is the most basic conversion method in organic synthesis chemistry. It is the simplest and most effective method to form new chemical bonds. It provides abundant carbon sources for the construction of a variety of compounds. This field has always been a hot topic for chemists. As the environmental pollution and energy crisis caused by the chemical industry become more and more serious, the exploration of reaction conditions is more mild (ideal reaction conditions at room temperature), and energy is more economical. In order to realize the functionalization of olefin and develop the sustainable development, it is an inevitable trend for the environmental friendly transition metal catalyst to realize the functionalization of olefin with large natural abundance and environmental friendly transition metal catalyst. The research content of this thesis is mainly based on this background. It is divided into two chapters and four sections to introduce the research of olefin functionalization reaction developed by these strategies. The specific contents are as follows: 1. A method for the synthesis of multifunctional dihydropyrrole derivatives by selective formation of C-N/C-C bond in the next step of reaction promoted by visible light has been developed. The reaction is easy to operate, the reaction conditions are mild, and the substrate is widely applicable. It is worth mentioning that the reaction can easily be scaled up to the gram scale, with strong practicality. Using this method, the multifunctional dihydropyrrole core skeleton can be obtained by a simple one-step reaction. Based on this strategy, a visible light to promote the formation of imine radical intermediates was developed. The hydroimide products and the oxyimide products were obtained by intramolecular cyclization of non-activated olefin in two different ways. The strategy is to efficiently synthesize 3'4-dihydropyrrole derivatives by constructing C-N bond. The reaction system has a wide range of substrates, and can obtain the target product by better yield. A method for the preparation of cis-2n-5-disubstituted pyrrolidine derivatives with transition metal copper catalyzed cyclization of non-active olefin was developed. The cis products prepared by this method can be further derivatized, which provides an effective way for the synthesis of drug molecules or natural products containing cis-2n 5-disubstituted pyrrole structure. 4. Finally, we developed the arylation of difluorinated olefins catalyzed by transition metal manganese through C-H bond activation and C-F bond breaking. The E-type products prepared by this method can be separated from the E / Z mixed products as the main products. The synthesis of E-type monofluoroolefins by C-H bond activation is reported for the first time. Our strategy not only complements the reaction type of transition metal manganese catalyst system, but also provides an alternative method for the preparation of fluorinated olefins.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.251
，
本文编号：2418639
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