本文關鍵詞： 鈀催化 釕催化 導向基 碳氫活化 羰基化 氟甲基化　出處：《中國科學技術大學》2017年博士論文　論文類型：學位論文

【摘要】：近些年來,過渡金屬催化的碳氫活化反應廣泛應用于有機材料、天然產物、藥物分子以及精細化學品的合成和制備中。在這些反應中,尤其是配體導向的碳氫活化反應因為無需預官能團化、原子經濟性等優(yōu)點,可以有效地縮短反應步驟,提高反應效率,激發(fā)了研究者的濃厚興趣。盡管配體導向的碳氫活化方面的研究成果報道了很多,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C-H鍵活化。因此,導向基的引入和選擇顯得至關重要。本論文主要集中在包括鈀催化或釕催化的含氮配體導向的sP2C-H活化反應,具體包括以下內容:1、發(fā)展了鈀催化的偶氮苯作為導向基的脫羧�；磻�。該反應提供了一系列鄰位�；姆菍ΨQ偶氮苯化合物,對氯、溴、碘和甲氧基等很多官能團都具有良好的適應性。另外,對位取代、鄰位取代和雙取代的偶氮苯均可以適應該體系。2、首次實現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。這個方法拓展了最近非常流行的乙酯化。不同的導向基,如肟醚和吡啶,都可以被用在該反應中。另外,這個體系官能團適應性非常好。該反應得到的產物也可以通過簡單的操作轉化為酮和內酯類化合物。3、成功實現了 2-苯氧基吡啶導向的脫羧酯基化反應。該反應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)導向的間位選擇性的氟甲基化反應。這個工作同時擴展了最近廣受關注的氟甲基化和釕催化的間位C-H活化反應的概念和范圍。另外,這個方法對于無氟的溴乙酸乙酯也可以實現間位C-H活化反應。
[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

【相似文獻】

相關期刊論文 前10條

1 陸培溪;;脂肪醛α-亞甲基化反應產物在香料工業(yè)中的應用[J];江蘇化工;1989年03期

2 王崢;酚的甲基化反應[J];中國醫(yī)藥工業(yè)雜志;2003年09期

3 顏杰;易家寶;;芳環(huán)上的直接三氟甲基化反應[J];四川理工學院學報(自然科學版);2009年01期

4 馮永輝;王克苗;;咖啡因甲基化反應工藝思路探索[J];科技傳播;2012年04期

5 王德o，

本文編號：1549496