本文選題：鐵卡賓　切入點(diǎn)：氨　出處：《華東師范大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：作為地殼中含量最多的過(guò)渡金屬,鐵具有廉價(jià)、安全等優(yōu)勢(shì)。利用鐵催化來(lái)代替貴重金屬催化成為合成化學(xué)家關(guān)注的焦點(diǎn)之一。雖然鐵催化分解重氮的反應(yīng)自上世紀(jì)90年代才被發(fā)現(xiàn),并且這方面的研究報(bào)道較少。鐵催化劑在催化卡賓轉(zhuǎn)移反應(yīng)中已經(jīng)表現(xiàn)出非常好的催化性能,鐵的配合物可以與重氮形成鐵卡賓,進(jìn)而發(fā)生一系列的轉(zhuǎn)化,如環(huán)丙烷化反應(yīng),插入反應(yīng)等。在已有的報(bào)道中,螺環(huán)雙VA唑啉配體與鐵形成的配合物在不對(duì)稱O-H插入反應(yīng)中取得了非常優(yōu)異的對(duì)映選擇性。同時(shí),卟啉鐵在N-H插入過(guò)程中表現(xiàn)出非常好的選擇性控制。本論文主要圍繞將鐵催化應(yīng)用于多組分反應(yīng)中以及相關(guān)機(jī)理的研究。論文的第一章前言介紹了鐵卡賓、親電試劑捕捉活性葉立德和離子對(duì)活性中間體的多組分反應(yīng)以及氨在有機(jī)合成中的應(yīng)用等內(nèi)容。同時(shí),對(duì)該論文的研究思路也做了介紹。論文的第二章的研究首次實(shí)現(xiàn)了對(duì)于重氮和脂肪胺形成的銨基葉立德的捕捉的三組分反應(yīng)。反應(yīng)的成功實(shí)現(xiàn)證明了脂肪胺的插入反應(yīng)經(jīng)過(guò)了葉立德過(guò)程并且該反應(yīng)提供了高效合成β-羥基α-氨基酸酯結(jié)構(gòu)的方法。論文的第三章實(shí)現(xiàn)了親電試劑靛紅對(duì)于重氮和氨形成的葉立德捕捉過(guò)程,實(shí)現(xiàn)了利用廉價(jià)易得的工業(yè)原料氨合成高附加值一級(jí)胺的反應(yīng)。該過(guò)程具有非常好的化學(xué)選擇性。并且通過(guò)控制實(shí)驗(yàn)我們發(fā)現(xiàn)產(chǎn)物的位阻效應(yīng)決定了反應(yīng)的化學(xué)選擇性。論文的第四章的研究是對(duì)于反應(yīng)機(jī)理的探究,我們合成并且通過(guò)單晶結(jié)構(gòu)表征了吸電子基團(tuán)鐵卡賓結(jié)構(gòu),這是首例吸電子取代鐵卡賓晶體的報(bào)道。并且我們首次實(shí)現(xiàn)了合成出來(lái)的鐵卡賓對(duì)于胺的N-H插入過(guò)程,證明了卟啉鐵催化的N-H插入反應(yīng)經(jīng)過(guò)了卡賓中間體過(guò)程。同時(shí)我們還實(shí)現(xiàn)了吸電子鐵卡賓與苯胺形成的葉立德的親電捕捉過(guò)程,證明了三組分反應(yīng)過(guò)程也經(jīng)歷了鐵卡賓中間體過(guò)程。論文第五章的研究是無(wú)金屬催化的重氮的鹵代反應(yīng)。該反應(yīng)可用于高效構(gòu)建3-鹵代氧化吲哚結(jié)構(gòu)和烯基鹵代物。該反應(yīng)具有非常好的普適性,我們順利實(shí)現(xiàn)了重氮酰胺的氟代,氯代,溴代和碘代。我們還實(shí)現(xiàn)了 3-溴代氧化吲哚的克級(jí)規(guī)模合成。
[Abstract]:As the most abundant transition metal in the earth's crust, iron is cheap. Safety and other advantages. The use of iron instead of precious metal catalysis has become one of the focuses of synthetic chemists. Although iron catalyzed decomposition of diazo was only discovered in -10s, Iron catalysts have shown very good catalytic performance in the carbene transfer reaction. Iron complexes can form tecabine with diazo and then undergo a series of transformations, such as cyclopropanation. In previous reports, the complexes formed by spirocyclic bis (VA) azoline ligands with iron obtained excellent enantioselectivity in asymmetric O-H insertion reactions. Porphyrin iron shows very good selective control during N-H insertion. In this paper, the application of iron catalyst in multicomponent reactions and related mechanisms are studied. The electrophilic reagents capture the multicomponent reaction of active Ylide and ion-pair active intermediates and the application of ammonia in organic synthesis. In the second chapter, the capture reaction of ammonium ylide formed by diazo and aliphatic amine was realized for the first time. The successful realization of the reaction proved the insertion of aliphatic amine. The entry reaction went through the Ylide process and provided an efficient method for the synthesis of 尾 -hydroxyl 偽 -amino acid esters. In chapter 3, the electrophilic reagent indirubin was used to capture the formation of diazo and ammonia. The synthesis of high value-added amine from ammonia, a cheap and easily available industrial raw material, has been realized. This process has very good chemical selectivity. By controlling the experimental results, we find that the reaction chemistry is determined by the steric resistance effect of the product. Selectivity. Chapter 4th of the paper is devoted to exploring the mechanism of the reaction. We have synthesized and characterized the structure of the ircarbene group by single crystal structure, which is the first report of the substitution of the electron absorption group for the iron carbene crystal, and we have realized the N-H insertion process of the synthesized iron carbene for amine for the first time. It is proved that the N-H intercalation reaction catalyzed by iron porphyrin has gone through the carbene intermediate process, and we have also realized the electrophilic trapping process of Ylide formed by the formation of iron carbene and aniline. It has been proved that the three component reaction process also experienced the intermediate process of iron carbene. Chapter 5th is a metal-free diazo halogenation reaction. This reaction can be used to efficiently construct the structure of 3-halogenated indoles and alkenyl halogenates. The reaction is very general, We have successfully achieved the fluorination, chlorination, bromination and iodization of diazoamides.
【學(xué)位授予單位】：華東師范大學(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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