本文關(guān)鍵詞： 鈀催化 釕催化 導(dǎo)向基 碳?xì)浠罨?羰基化 氟甲基化　出處：《中國科學(xué)技術(shù)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：近些年來,過渡金屬催化的碳?xì)浠罨磻?yīng)廣泛應(yīng)用于有機(jī)材料、天然產(chǎn)物、藥物分子以及精細(xì)化學(xué)品的合成和制備中。在這些反應(yīng)中,尤其是配體導(dǎo)向的碳?xì)浠罨磻?yīng)因為無需預(yù)官能團(tuán)化、原子經(jīng)濟(jì)性等優(yōu)點,可以有效地縮短反應(yīng)步驟,提高反應(yīng)效率,激發(fā)了研究者的濃厚興趣。盡管配體導(dǎo)向的碳?xì)浠罨矫娴难芯砍晒麍蟮懒撕芏?但是仍然面臨著巨大的挑戰(zhàn)。一方面,C-H鍵的能量普遍高于C-C鍵、C-X鍵、H-X鍵,因此如何克服較高的能壘實現(xiàn)C-H鍵活化就成為一個重要的議題。另一方面,C-H鍵能量差異很小,因此如何控制反應(yīng)的選擇性就顯得尤為重要。后過渡金屬因為d軌道和p軌道未充滿,可以與孤電子對或π電子相互作用,可以較容易地實現(xiàn)C-H鍵活化。因此,導(dǎo)向基的引入和選擇顯得至關(guān)重要。本論文主要集中在包括鈀催化或釕催化的含氮配體導(dǎo)向的sP2C-H活化反應(yīng),具體包括以下內(nèi)容:1、發(fā)展了鈀催化的偶氮苯作為導(dǎo)向基的脫羧酰基化反應(yīng)。該反應(yīng)提供了一系列鄰位�；姆菍ΨQ偶氮苯化合物,對氯、溴、碘和甲氧基等很多官能團(tuán)都具有良好的適應(yīng)性。另外,對位取代、鄰位取代和雙取代的偶氮苯均可以適應(yīng)該體系。2、首次實現(xiàn)了鈀催化的利用草酸單乙酯作為酯基來源這一新穎、高效的C-H酯基化反應(yīng)。這個方法拓展了最近非常流行的乙酯化。不同的導(dǎo)向基,如肟醚和吡啶,都可以被用在該反應(yīng)中。另外,這個體系官能團(tuán)適應(yīng)性非常好。該反應(yīng)得到的產(chǎn)物也可以通過簡單的操作轉(zhuǎn)化為酮和內(nèi)酯類化合物。3、成功實現(xiàn)了 2-苯氧基吡啶導(dǎo)向的脫羧酯基化反應(yīng)。該反應(yīng)可以得到一系列水楊酸乙酯類衍生物。并且,作為一種普適和簡便的方法,該反應(yīng)可以為合成阿司匹林衍生物提供一種新的策略和思路。4、發(fā)展了首例釕催化的含氮芳香雜環(huán)導(dǎo)向的間位選擇性的氟甲基化反應(yīng)。這個工作同時擴(kuò)展了最近廣受關(guān)注的氟甲基化和釕催化的間位C-H活化反應(yīng)的概念和范圍。另外,這個方法對于無氟的溴乙酸乙酯也可以實現(xiàn)間位C-H活化反應(yīng)。
[Abstract]:In recent years, the transition metal catalyzed C-H activation reactions are widely used in organic materials, natural products, drug molecules and the synthesis and preparation of fine chemicals synthesis. In these reactions, especially ligand directed C-H activation reactions because no officer group, has the advantages of atom economy, can effectively shorten the reaction steps to improve the reaction efficiency, strong interest, inspire researchers. Although ligand directed C-H activation studies reported a lot, but still faces huge challenges. On the one hand, the C-H bond energy is generally higher than that of the C-C key, C-X key, H-X key, so how to overcome the energy barrier of C-H bond activation has become an important issue is higher. On the other hand, the C-H key energy difference is very small, so how to control the reaction selectivity is particularlyimportant. Transition metal because the D track and P track is not full, and can Lonepairelectrons or pi electron interaction, it is easy to implement C-H activation. Therefore, the guide base and the introduction of choice is very important. This paper mainly focus on including palladium catalyzed or ruthenium catalyzed nitrogen ligand directed sP2C-H activation, including the following: 1, the development of the palladium catalyzed azobenzene as the guide base decarboxylation of acylation reaction. This reaction provides asymmetric azobenzene compounds, a series of ortho acylation of chlorine, bromine, iodine and methoxy groups have good adaptability of many functional groups. In addition, para substituted ortho substituted and disubstituted azobenzene can adapt to the system of.2 for the first time. The palladium catalyzed by oxalic acid ethyl ester as the single source of this novel, C-H ester reaction efficiency. This method provides a very popular recently. Based on different orientation of ethyl ester, such as oxime ether and pyridine, can To be used in the reaction. In addition, the system of functional adaptability is very good. The product of this reaction can also be through simple operation into ketones and lactones.3, the successful implementation of the decarboxylation reaction of 2- ester phenoxy pyridine oriented. This reaction can get a series of ethyl salicylate derivatives and, as a universal and convenient method, the reaction may provide a new strategy for the synthesis of aspirin and thought of.4 derivatives, the first development of ruthenium catalyzed aromatic azacyclo oriented a selective difluoromethylation reaction. The concept and scope of the work of the C-H activation and expansion difluoromethylation and ruthenium catalyzed wide concern among recently. In addition, this method can achieve a C-H activation reaction for ethyl bromide without fluorine.

【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O621.251

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本文編號：1549496