【摘要】：烯烴的官能化反應是有機合成化學中最為基本的一種轉化方式,是形成新化學鍵最為簡單有效的方法,為構建多種多樣的化合物骨架提供了豐富的碳源,該領域一直是化學家研究的熱點。隨著化學工業(yè)生產(chǎn)中造成的環(huán)境污染和能源危機問題越來越嚴重,使得探索反應條件更為溫和(理想反應條件室溫)、能源更為節(jié)約、對環(huán)境更為友好的反應體系去實現(xiàn)烯烴的官能化以及開發(fā)可持續(xù)發(fā)展、天然豐度大、環(huán)境友好的過渡金屬催化劑進行烯烴官能化反應成為必然趨勢。本論文的研究內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)展起來的烯烴官能化反應的研究,具體內容如下:1.發(fā)展了在可見光促進下一步反應選擇性生成C-N/C-C鍵用以合成多官能化二氫吡咯衍生物的方法。該反應操作簡便、反應條件溫和、底物適用性廣。值得一提的是,該反應可以很容易地放大到克級規(guī)模,具有很強的實用性。應用此方法可以通過簡單的一步反應得到多官能化的二氫吡咯核心骨架。2.基于該策略,同時發(fā)展了一種可見光促進生成亞胺自由基中間體,通過分子內環(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構建C-N鍵高效合成3,4-二氫吡咯衍生物。該反應體系底物范圍廣,并都能以較好到優(yōu)異的產(chǎn)率得到目標產(chǎn)物。3.發(fā)展了過渡金屬銅催化環(huán)化非活化烯烴制備順式-2,5-二取代吡咯烷類衍生物的方法。利用該方法制備的順式產(chǎn)物可以進一步衍生化,為合成含順式-2,5-二取代吡咯結構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)展了過渡金屬錳催化下通過C-H鍵活化、C-F鍵斷裂途徑的偕二氟烯烴的芳基化反應。本次報道的方法制備的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,通過C-H鍵活化合成E式單氟烯烴是首次報道。我們本次發(fā)展的策略補充了過渡金屬錳催化體系的反應類型的同時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.
【學位授予單位】：中國科學技術大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O621.251
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本文編號：2418639