本文關(guān)鍵詞： 銥 sp~3C-H鍵 芳基化 肟醚 二芳基高碘化物 sp~2C-H鍵 含氮雜環(huán) 烯烴　出處：《揚(yáng)州大學(xué)》2016年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：研究生期間我的研究?jī)?nèi)容主要分為以下三個(gè)部分：].銥催化sp3C-H鍵直接芳基化反應(yīng)的研究過(guò)渡金屬催化活化碳?xì)滏I的方法已經(jīng)成為有機(jī)合成中不可或缺的一部分,近年來(lái)該領(lǐng)域已受到化學(xué)界的高度關(guān)注。脂肪族的碳?xì)滏I廣泛存在于有機(jī)分子中,如何高效和高選擇性的實(shí)現(xiàn)其官能團(tuán)化,構(gòu)建新的碳碳鍵和碳雜原子鍵,至今仍然是一個(gè)巨大的挑戰(zhàn)。在過(guò)渡金屬催化下,可以實(shí)現(xiàn)直接碳?xì)滏I的芳基化,這相對(duì)于傳統(tǒng)的有機(jī)合成方法有著巨大的優(yōu)勢(shì),能夠克服傳統(tǒng)方法中需要多步才能實(shí)現(xiàn)的反應(yīng)。β芳基化的酮肟是可以轉(zhuǎn)換為許多天然產(chǎn)物和藥物分子的重要結(jié)構(gòu)單元,我們利用三價(jià)銥金屬配合物作為催化劑,芳基高碘化物作為芳基源,首次成功通過(guò)sp3 C-H鍵活化實(shí)現(xiàn)了在肟醚β位引入芳基的反應(yīng)。該方法具有原子經(jīng)濟(jì)、較好的反應(yīng)底物兼容性和較高的區(qū)域選擇性等特點(diǎn)。最后通過(guò)密度泛函理論(DFT)計(jì)算,從理論的角度解釋了反應(yīng)的形成過(guò)程。2.銥催化含氮雜環(huán)化合物直接芳基化反應(yīng)研究雜環(huán)化合物包括吡啶,吡嗪,喹啉,吡唑,異惡唑等是許多藥物以及生物活性分子中常見(jiàn)的結(jié)構(gòu),我們?cè)O(shè)想一種可靠的雜環(huán)化合物直接芳基化方法將會(huì)意義重大。我們通過(guò)不斷的探索和反應(yīng)條件的優(yōu)化,尋找出最佳的反應(yīng)條件。利用[IrCp*Cl2]2作為催化劑,AgNTf2作為添加劑,PivOH,4A MS和溶劑環(huán)己烷,二芳基高碘化物作為芳基源,在1000C條件下成功實(shí)現(xiàn)了雜環(huán)化合物的芳基化。在該反應(yīng)體系下,得到的是單一的單取代芳基化產(chǎn)物,并且通過(guò)GC-MS沒(méi)有觀測(cè)到二取代的副產(chǎn)物。該轉(zhuǎn)化不僅能夠兼容六元雜環(huán),五元雜環(huán)也可以得到較高產(chǎn)率的芳基化產(chǎn)物。該轉(zhuǎn)化對(duì)于修飾藥物以及生物活性分子具有很好的實(shí).用價(jià)值和應(yīng)用前景。3.芳基以及烯基化合物鄰位C-H鍵直接芳基化研究盡管sp2 C-H鍵的直接芳基化反應(yīng)已經(jīng)被深入的研究,包括使用Pd,Ni,Cu,Ru,Rh等過(guò)渡金屬,但是Ir(Ⅲ)催化芳香化合物的直接芳基化反應(yīng)仍然很少。我們利用半三明治結(jié)構(gòu)的三價(jià)銥配合物作為催化劑,成功實(shí)現(xiàn)了芳基化合物的sp2C-H鍵的芳基化,該反應(yīng)體系具有非常高的官能團(tuán)兼容性。包括吡啶類(lèi)化合物,酰胺類(lèi)化合物以及肟醚類(lèi)化合物都能很好的得到芳基化的目標(biāo)產(chǎn)物。同時(shí),烯基類(lèi)化合物在酰胺,肟醚以及羧酸的導(dǎo)向基團(tuán)存在下能夠順利的實(shí)現(xiàn)C-H鍵的芳基化。值得注意的是,這些偶聯(lián)反應(yīng)發(fā)生完全得到的是Z式。這種立體選擇性是非常有價(jià)值的,因?yàn)樗哂袧撛诘暮铣蓱?yīng)用。
[Abstract]:As a graduate student, my research is mainly divided into the following three parts:] .Iridium catalyzed direct arylation of sp3C-H bond; transition metal catalytic activation of hydrocarbon bonds has become an indispensable part of organic synthesis. In recent years, this field has attracted great attention in chemistry. Aliphatic carbon-hydrogen bonds are widely found in organic molecules. How to efficiently and selectively realize their functionalization and construct new carbon-carbon bonds and carbon hetero-atomic bonds. It is still a huge challenge. Arylation of direct hydrocarbon bonds can be achieved under the catalysis of transition metals, which has great advantages over traditional organic synthesis methods. The ketone oxime of 尾 arylation is an important structural unit that can be converted into many natural products and drug molecules. We use the metal complexes of iridium trivalent as the catalyst. Aryl polyiodides as aryl sources were successfully activated by sp3 C-H bond for the first time to realize the introduction of aryl groups to the 尾 site of oxime ether. Better substrate compatibility and higher regioselectivity. Finally, the density functional theory (DFT) is used to calculate, The formation process of the reaction was explained theoretically. 2. Direct arylation of heterocyclic compounds containing nitrogen catalyzed by iridium; heterocyclic compounds including pyridine, pyrazine, quinoline, pyrazole, pyrazole, pyrazine, pyrazine, pyrazine, pyrazine, pyrazine. Isoxazole and so on are common structures in many drugs and bioactive molecules, so it would be important to imagine a reliable method of direct arylation of heterocyclic compounds. Using [IrCp*Cl2] 2 as catalyst and solvent cyclohexane as additive, the arylation of heterocyclic compounds was successfully realized at 1000C by using [IrCp*Cl2] 2 as catalyst and solvent cyclohexane and diaryl polyiodide as aryl source. A single monosubstituted arylation product was obtained, and no disubstituted by-products were observed by GC-MS. High yield arylation products can also be obtained from quaternary heterocyclic compounds. The conversion has a good effect on modifying drugs and bioactive molecules. The value and application prospect. 3. Aryl group and direct aryl group of O-C-H bond of alkenyl compounds. Although the direct arylation of sp2 C-H bonds has been studied in depth, The direct arylation of aromatic compounds catalyzed by Ir- (鈪，

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