基于光致氧化還原和過(guò)渡金屬催化的烯烴官能化反應(yīng)的研究
發(fā)布時(shí)間：2019-02-08 17:45
【摘要】：烯烴的官能化反應(yīng)是有機(jī)合成化學(xué)中最為基本的一種轉(zhuǎn)化方式,是形成新化學(xué)鍵最為簡(jiǎn)單有效的方法,為構(gòu)建多種多樣的化合物骨架提供了豐富的碳源,該領(lǐng)域一直是化學(xué)家研究的熱點(diǎn)。隨著化學(xué)工業(yè)生產(chǎn)中造成的環(huán)境污染和能源危機(jī)問(wèn)題越來(lái)越嚴(yán)重,使得探索反應(yīng)條件更為溫和(理想反應(yīng)條件室溫)、能源更為節(jié)約、對(duì)環(huán)境更為友好的反應(yīng)體系去實(shí)現(xiàn)烯烴的官能化以及開(kāi)發(fā)可持續(xù)發(fā)展、天然豐度大、環(huán)境友好的過(guò)渡金屬催化劑進(jìn)行烯烴官能化反應(yīng)成為必然趨勢(shì)。本論文的研究?jī)?nèi)容主要就是基于此背景確定的選題,分兩章四小節(jié)介紹了利用這些策略發(fā)展起來(lái)的烯烴官能化反應(yīng)的研究,具體內(nèi)容如下:1.發(fā)展了在可見(jiàn)光促進(jìn)下一步反應(yīng)選擇性生成C-N/C-C鍵用以合成多官能化二氫吡咯衍生物的方法。該反應(yīng)操作簡(jiǎn)便、反應(yīng)條件溫和、底物適用性廣。值得一提的是,該反應(yīng)可以很容易地放大到克級(jí)規(guī)模,具有很強(qiáng)的實(shí)用性。應(yīng)用此方法可以通過(guò)簡(jiǎn)單的一步反應(yīng)得到多官能化的二氫吡咯核心骨架。2.基于該策略,同時(shí)發(fā)展了一種可見(jiàn)光促進(jìn)生成亞胺自由基中間體,通過(guò)分子內(nèi)環(huán)化非活化烯烴再分兩種不同的途徑分別得到氫亞胺化產(chǎn)物和氧亞胺化產(chǎn)物的方法。該策略主要在于通過(guò)構(gòu)建C-N鍵高效合成3,4-二氫吡咯衍生物。該反應(yīng)體系底物范圍廣,并都能以較好到優(yōu)異的產(chǎn)率得到目標(biāo)產(chǎn)物。3.發(fā)展了過(guò)渡金屬銅催化環(huán)化非活化烯烴制備順式-2,5-二取代吡咯烷類(lèi)衍生物的方法。利用該方法制備的順式產(chǎn)物可以進(jìn)一步衍生化,為合成含順式-2,5-二取代吡咯結(jié)構(gòu)的藥物分子或者天然產(chǎn)物提供一種有效的途徑。4.最后,我們發(fā)展了過(guò)渡金屬錳催化下通過(guò)C-H鍵活化、C-F鍵斷裂途徑的偕二氟烯烴的芳基化反應(yīng)。本次報(bào)道的方法制備的E式產(chǎn)物作為主產(chǎn)物可以從E/Z混合產(chǎn)物中分離出來(lái),通過(guò)C-H鍵活化合成E式單氟烯烴是首次報(bào)道。我們本次發(fā)展的策略補(bǔ)充了過(guò)渡金屬錳催化體系的反應(yīng)類(lèi)型的同時(shí)也為制備氟化烯烴提供了一種可替代的方法。
[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.
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O621.251
，
本文編號(hào)：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.
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O621.251
，
本文編號(hào)：2418639
本文鏈接：http://sikaile.net/shoufeilunwen/gckjbs/2418639.html
最近更新
教材專(zhuān)著
