本文選題：碳碳鍵形成 + 碳?xì)滏I活化　； 參考：《中國(guó)科學(xué)技術(shù)大學(xué)》2017年博士論文

【摘要】：碳碳鍵的形成是有機(jī)合成中產(chǎn)生分子復(fù)雜性的最根本方式之一。這一領(lǐng)域從一開始便得到了化學(xué)家們的廣泛關(guān)注,從而發(fā)展出了眾多不同的轉(zhuǎn)化方法以構(gòu)筑碳碳鍵。以碳(sp3)為中心的飽和碳-碳鍵在工業(yè)原材料,藥物以及天然產(chǎn)物中的存在較為廣泛。因此發(fā)展飽和碳-碳鍵構(gòu)筑方法顯得尤為重要。推進(jìn)反應(yīng)發(fā)展的重要前提是對(duì)催化反應(yīng)機(jī)理具備深入了解。掌握反應(yīng)機(jī)理有助于不斷提升現(xiàn)有催化反應(yīng)效率,理性設(shè)計(jì)新反應(yīng)及新催化體系。隨著計(jì)算機(jī)技術(shù)的發(fā)展,以及量子理論新方法的不斷創(chuàng)新,理論計(jì)算方法已經(jīng)成為獲取機(jī)理信息的重要方式。本論文采用理論計(jì)算方法,針對(duì)若干飽和碳碳鍵構(gòu)筑反應(yīng)的機(jī)理展開系統(tǒng)研究。論文第一部分綜述了有機(jī)合成領(lǐng)域構(gòu)筑飽和碳碳鍵的主要方法。第一類為過渡金屬催化的偶聯(lián)反應(yīng),分為交叉偶聯(lián)、氧化偶聯(lián)和還原偶聯(lián)。第二類為基于過渡金屬催化碳(sp3)-氫鍵活化的碳碳鍵形成,詳細(xì)介紹了通過該方法構(gòu)筑碳(sp3)-碳(sp2)鍵、碳(sp3)-碳(sp3)鍵和碳(sp3)-碳(sp)鍵的研究進(jìn)展。第三類為過渡金屬催化烯烴雙官能團(tuán)化構(gòu)筑碳碳鍵,這里主要介紹了通過金催化劑實(shí)現(xiàn)的分子內(nèi)和分子間的雙官能化。第四類屬于非金屬催化領(lǐng)域,主要介紹通過卡賓催化劑實(shí)現(xiàn)的高烯醇化反應(yīng)構(gòu)筑碳碳鍵。最后對(duì)研究上述反應(yīng)機(jī)理所需的理論方法,包括密度泛函方法、基組和溶劑化模型進(jìn)行介紹。論文第二部分介紹了鈀催化胺甲酰氯選擇性碳(sp3)-氫鍵活化�；瘶�(gòu)筑碳(sp3)-碳(sp2)鍵的機(jī)理研究結(jié)果。研究表明反應(yīng)經(jīng)歷的是"氧化加成/碳?xì)滏I活化/還原消除"機(jī)理。碳?xì)浠罨欠磻?yīng)的選擇性決定步驟。發(fā)現(xiàn)添加劑能夠提高反應(yīng)速率,但不決定選擇性。芐基碳?xì)滏I酸性高于芳基碳?xì)滏I,因此碳?xì)滏I酸性是選擇性的決定因素。論文第三部分介紹了光-金雙催化的烯烴氧芳基化反應(yīng)的機(jī)理研究結(jié)果。研究發(fā)現(xiàn)光催化循環(huán)經(jīng)歷氧化淬滅歷程。金催化循環(huán)中"自由基氧化/單電子氧化/底物絡(luò)合/環(huán)化/還原消除"機(jī)理最為優(yōu)勢(shì)。上述機(jī)理優(yōu)勢(shì)的原因在于:Au(Ⅲ)絡(luò)合物的環(huán)化有利(降低了烯烴的LUMO軌道能量);苯基自由基向Au(Ⅰ)中心轉(zhuǎn)移一部分電子的過程使得自由基加成-SET的機(jī)理順序有利。論文第四部分介紹了卡賓催化αα,β-不飽和酮與硝基烯烴高烯醇化反應(yīng)的機(jī)理研究結(jié)果。結(jié)果表明反應(yīng)經(jīng)歷"Breslow中間體形成/對(duì)硝基烯烴的親核進(jìn)攻/分子內(nèi)質(zhì)子轉(zhuǎn)移/HOAc參與的質(zhì)子化/協(xié)同的OEt對(duì)羰基的親核進(jìn)攻/卡賓解離"的機(jī)理過程。高烯醇化路徑優(yōu)于Stetter路徑的原因是關(guān)鍵中間體的熱力學(xué)穩(wěn)定性,以及分子內(nèi)質(zhì)子轉(zhuǎn)移和OEt對(duì)羰基親核進(jìn)攻的動(dòng)力學(xué)優(yōu)勢(shì)。另外,高烯醇化路徑的立體選擇性決定步驟是Breslow中間體對(duì)硝基烯烴的進(jìn)攻。其中位阻效應(yīng)和氫鍵決定了 syn構(gòu)型的立體選擇性。
[Abstract]:The formation of carbon-carbon bond is one of the most fundamental ways to produce molecular complexity in organic synthesis. This field has been widely concerned by chemists from the beginning, and many different conversion methods have been developed to construct carbon and carbon bonds. The saturated carbon-carbon bond with carbon sp3 as its center is widely used in industrial raw materials, drugs and natural products. Therefore, the development of saturated carbon-carbon bond construction is particularly important. An important prerequisite for promoting the development of reaction is to have a thorough understanding of the mechanism of catalytic reaction. Mastering the reaction mechanism is helpful to improve the efficiency of existing catalytic reactions and to rationally design new reactions and new catalytic systems. With the development of computer technology and the innovation of new methods of quantum theory, theoretical calculation method has become an important way to obtain mechanism information. In this paper, the theoretical calculation method is used to study the mechanism of some saturated carbon bond construction reactions. In the first part, the main methods of constructing saturated carbon bond in organic synthesis are reviewed. The first type is transition metal catalyzed coupling reaction, which is divided into cross coupling, oxidative coupling and reduction coupling. The second kind is the formation of carbon bond based on transition metal catalyzed carbon sp3-hydrogen bond. The progress in the construction of carbon sp3tium-carbon sp2 bond, carbon sp3tium-carbon sp3 bond and carbon sp3- carbon sp3 bond by this method is introduced in detail. The third is transition metal catalyzed bifunctional alkenes to form carbon-carbon bonds. In this paper, intramolecular and intermolecular difunctionalization by gold catalysts is introduced. The fourth category belongs to the field of non-metallic catalysis. It mainly introduces the formation of carbon bond by the high-enolization reaction of carbene catalyst. Finally, the theoretical methods needed to study the above reaction mechanism, including density functional method, basis group and solvation model, are introduced. In the second part of this paper, the mechanism of palladium catalyzed activation and acylation of carbamoyl chloride selective carbon-sp3a-hydrogen bond to form carbon-sp3- carbon-sp2 bond is introduced. It has been shown that the reaction goes through the mechanism of "oxidation addition / carbon bond activation / reduction elimination". Hydrocarbon activation is the selective determining step of the reaction. It was found that the additive could increase the reaction rate but not determine the selectivity. The acidity of benzyl hydrocarbon bond is higher than that of aryl hydrocarbon bond, so the acidity of hydrocarbon bond is the determinant of selectivity. In the third part of this paper, the mechanism of photo-gold-catalyzed olefin arylation is introduced. It is found that the photocatalytic cycle goes through the process of oxidation quenching. The mechanism of "free radical oxidation / single electron oxidation / substrate complexation / cyclization / reduction elimination" is the most advantageous mechanism in the gold catalytic cycle. The above mechanism advantage lies in the favorable cyclization of the 1: Au3 complex (which reduces the LUMO orbital energy of olefins), and the transfer of some electrons from the phenyl radical to the center of Au1 (I), which makes the mechanism of radical addition-SET favorable. In the fourth part of the paper, the mechanism of 偽, 尾 -unsaturated ketones catalyzed by carbene for high enolefin reaction with nitroolefins was introduced. The results show that the reaction goes through the mechanism of "Breslow intermediate formation / nucleophilic attack of p-nitroolefin / intramolecular proton transfer / protonation / synergistic OEt nucleophilic attack on carbonyl group / carbene dissociation". The high enolation path is superior to the Stetter path because of the thermodynamic stability of the key intermediates and the kinetic advantages of intramolecular proton transfer and OEt on the nucleophilic attack of carbonyl groups. In addition, the step of stereoselectivity determination of high enolefin pathway is the attack of Breslow intermediate p-nitroolefin. The stereoselectivity of syn configuration is determined by steric resistance and hydrogen bonding.
【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
【分類號(hào)】：O621.251

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