本文關(guān)鍵詞： 鎳 硼化 活化 碳-氮健 烯烴 高化學選擇性　出處：《南京大學》2017年博士論文　論文類型：學位論文

【摘要】：碳-氮鍵是最豐富的化學鍵之一,并且廣泛存在于許多有機分子和生物大分子中。碳-氮鍵高的離解能和穩(wěn)定性,使它們成為合成有機化學中最普遍的惰性有機化合物之一。毫無疑問,碳-氮鍵斷裂仍然是一個具有挑戰(zhàn)性的課題,并且將在未來的化學中引起極大的關(guān)注。由于易獲得的含氮化合物能提供優(yōu)異的氮源或碳源構(gòu)建有用的分子,因此,過渡金屬催化碳-氮鍵裂解已經(jīng)成為一個研究熱區(qū)。本課題組致力于發(fā)展惰性化學鍵的斷裂活化,使其進行官能團化,并取得了一定進展�；谖墨I和實驗研究基礎(chǔ),我的博士論文圍繞碳-氮鍵斷裂活化,且該轉(zhuǎn)化具有優(yōu)秀的化學選擇性,官能團兼容性和高的轉(zhuǎn)化效率。本論文的研究包括季銨鹽碳-氮鍵的直接硼化,酰胺的脫羰硼化和脂肪酰胺的脫羰β-氫消除,如下:第一部分:建立一種溫和的鎳催化體系,使sp~2和sp~3碳-氮鍵直接斷裂硼化。這高效的反應(yīng)主要取決于適合的化學體系:催化劑Ni(COD)2,配體ICy·HCl和乙二醇單甲醚共溶劑。而且,這轉(zhuǎn)化不僅具有較好的官能團兼容性,也能作為一種強大的有機合成方法。鑒于-NMe2基團及其羧酸前體在化學中的廣泛應(yīng)用,該方法提供了一種有意義的工具,使其成為有用的反應(yīng)模塊。由于這些優(yōu)點,該反應(yīng)應(yīng)具有高的合成價值。第二部分:建立一種鎳/氮雜卡賓催化體系,通過碳-氮鍵活化,使酰胺脫羰與B2nep2進行硼化。這轉(zhuǎn)化不僅能兼容各種官能團,也能作為一種強大的酰胺硼化合成方法。鑒于酰胺及其羧酸前體在化學中的廣泛應(yīng)用,該方法提供了有用的工具,以使得它們能夠作為有價值的結(jié)構(gòu)單元。更重要的是,首次分離得到金屬中間體(�；噺�(fù)合物),并通過X衍射證實其結(jié)構(gòu)。而且也觀察到其脫羰過程。這些研究證實了酰胺碳-氮鍵斷裂的關(guān)鍵機理過程。第三部分:酰胺和烯烴是具有可逆性的重要合成中間體,其在天然產(chǎn)物,藥物和人造材料的構(gòu)建中起關(guān)鍵作用。將高度穩(wěn)定的脂肪族酰胺直接轉(zhuǎn)化為烯烴是一項具有挑戰(zhàn)性的任務(wù)。本課題組建立一種鎳/氮雜卡賓催化體系,通過碳-氮和碳-碳鍵斷裂活化,使脂肪酰胺脫羰消除形成各種烯烴。這種方法不僅克服了脂肪酰胺碳-氮鍵的活化,而且創(chuàng)新了 一種獨特的消除反應(yīng),稱之為"retro-hydroamidocarbonylation"。這種化學轉(zhuǎn)化不僅能兼容各種官能團,也能作為一種強大有機方法學,使脂肪酰胺轉(zhuǎn)化為烯烴化合物。
[Abstract]:Carbon nitrogen bond is one of the most abundant chemical bonds, and widely exists in many organic molecules and biological macromolecules. The dissociation of carbon nitrogen bonds with high energy and stability, making them one of the most common inert organic compound in organic chemistry. There is no doubt that the carbon nitrogen bond rupture is still a a challenging task, and caused great concern in the future. Because of easily available chemical compounds containing nitrogen can provide excellent nitrogen or carbon source to construct useful molecules, therefore, transition metal catalyzed C-N bond cleavage has become a research hotspot. The activated fault research group is committed to the development of inertia the chemical bond, the functional groups, and some progress has been made. Based on literature and experimental research based on my PhD thesis on carbon nitrogen bond cleavage activation, and the conversion of chemical selectivity and excellent functional compatibility And high conversion efficiency. Direct boronation the research includes quaternary carbon nitrogen bond, decarbonylation of boron and fatty amide decarbonylation of hydride elimination, are as follows: the first part: the establishment of amide is a mild nickel catalyst system, the sp~2 and sp~3 direct fracture of boron carbon nitrogen bond. This high efficiency mainly depends on the chemical reaction system suitable for the catalyst Ni (COD) 2, ICy ligand - HCl and ethylene glycol monomethyl ether solvent. Moreover, this transformation not only has good functional compatibility, can also be used as a powerful method for organic synthesis. Given the wide application of -NMe2 group and its former carboxylic acid in chemistry, the method provides a useful tool to become useful reaction module. Because of these advantages, the reaction has high value of synthesis. The second part: the establishment of a nickel / aza CABBEEN catalyst system, the carbon nitrogen bond activation, the amide decarbonylation Boron and B2nep2. This transformation is not only compatible with various functional groups, and also can be used as a powerful method for synthesis of amide boride. Given the widely used amide and carboxylic acid precursor in chemistry, this method provides a useful tool, so that they can serve as a valuable structural unit is more important. For the first time, isolated metal intermediates (acyl nickel complex), and its structure was confirmed by X diffraction. And also observed the decarbonylation process. This study confirmed that the key mechanism of amide carbon nitrogen bond fracture. Third part: amide and olefins are important intermediates are reversible, in the natural construction products, drugs and artificial materials plays a key role. The highly stable aliphatic amide directly into olefins is a challenging task. This paper established a nickel / aza CABBEEN catalytic system, through carbon The activation of nitrogen and carbon carbon bond cleavage, the fatty amide decarbonylated eliminate the formation of various olefins. This method not only overcomes the activation of fatty acid amide carbon nitrogen bond, but also create a unique elimination reaction, called "retro-hydroamidocarbonylation". This conversion is not only compatible with various functional groups, and also can be used as a strong organic methodology, the fatty acid amide into alkenes.

【學位授予單位】：南京大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O621.251

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