本文選題：重氮化合物 + 金屬卡賓�。� 參考：《浙江大學(xué)》2017年博士論文

【摘要】：血紅素是自然界中含量最為豐富的天然鐵卟啉復(fù)合物,存在于多種血紅素蛋白中,承擔(dān)著重要的催化活性。近幾十年,以其為活性輔基的血紅素蛋白如肌紅蛋白、辣根過(guò)氧化物酶、細(xì)胞色素P450等被廣泛用于各種生物化學(xué)研究中,而血紅素自身卻很少被用于催化有機(jī)反應(yīng),尤其是非天然化學(xué)反應(yīng)。另一方面,以重氮化合物為前體的金屬卡賓是近些年的研究熱點(diǎn),它可以與親核試劑發(fā)生不同的轉(zhuǎn)化反應(yīng),如X-H插入反應(yīng)(X=N,S,O,C,Si,B...)、環(huán)丙烷化反應(yīng)和葉立德形成反應(yīng)等,在有機(jī)合成中有著重要的作用。本論文主要圍繞氯化血紅素在非天然卡賓化學(xué)中的催化作用展開(kāi),研究結(jié)果主要包括以下三個(gè)方面:水相中氯化血紅素-環(huán)糊精體系催化的N-H鍵插入反應(yīng):建立了氯化血紅素-環(huán)糊精水相催化體系,實(shí)現(xiàn)了水溶液中的αα-重氮酯與芳香胺類化合物的N-H鍵插入反應(yīng),含多種取代基的苯胺、萘胺、四氫吲哚都適用于該反應(yīng),產(chǎn)率最高可達(dá)96%。另外,通過(guò)調(diào)控環(huán)糊精腔體大小可以一定程度上調(diào)節(jié)苯胺與重氮乙酸乙酯的單N-H鍵插入產(chǎn)物和雙N-H鍵插入產(chǎn)物的比例。水相中氯化血紅素-環(huán)糊精-曲拉通X-100體系催化的硫葉立德的形成及其Doyle-Kirmse反應(yīng):通過(guò)在之前的氯化血紅素-環(huán)糊精體系中引入表面活性劑曲拉通X-100,實(shí)現(xiàn)了氯化血紅素在水相中催化重氮化合物和烯丙基硫醚產(chǎn)生硫葉立德,并進(jìn)一步發(fā)生Doyle-Kirmse重排反應(yīng)。該催化體系反應(yīng)條件溫和,具有優(yōu)良的底物普適性和良好的反應(yīng)產(chǎn)率,對(duì)非水溶性的芳基烯丙基硫醚或烷基烯丙基硫醚都適用。氯化血紅素催化的硫葉立德的形成及其底物控制的化學(xué)選擇性的[1,2]-Stevens和Sommelet-Hauser重排反應(yīng):通過(guò)對(duì)芐基硫醚的芐基上取代基電子效應(yīng)的控制和溶劑的選擇,實(shí)現(xiàn)了經(jīng)由血紅素卡賓產(chǎn)生的芐基硫葉立德選擇性地發(fā)生[1,2]-Stevens反應(yīng)和Sommelet-Hauser重排反應(yīng),給電子基團(tuán)或弱吸電子基團(tuán)取代的芐基硫醚易發(fā)生[1,2]-Stevens反應(yīng),而對(duì)位強(qiáng)吸電子基團(tuán)取代的芐基硫醚卻更易于發(fā)生Sommelet-Hauser反應(yīng),且水溶液和適當(dāng)降低溫度可以促進(jìn)Sommelet-Hauser反應(yīng)。
[Abstract]:Heme is the most abundant natural iron porphyrin complex in nature. It exists in a variety of heme proteins and plays an important catalytic role.In recent decades, heme proteins, such as myoglobin, horseradish peroxidase, cytochrome P450 and so on, have been widely used in various biochemical studies, but heme itself is rarely used to catalyze organic reactions.Especially unnatural chemical reactions.On the other hand, metal carbene with diazo compounds as precursor has been a hot research topic in recent years. It can undergo different conversion reactions with nucleophilic reagents, such as X-H insertion reaction, X ~ (2 +) -N ~ (2 +) ~ (2 +) -C ~ (2 +) SiB..0.The reaction of cyclopropanation and ylide formation, etc.Play an important role in organic synthesis.This paper focuses on the catalytic role of hemin in unnatural carbene chemistry.The results mainly include the following three aspects: the N-H bond insertion reaction catalyzed by hemin cyclodextrin system in water phase: the water phase catalytic system of hemin cyclodextrin was established.The N-H bond insertion reaction of 偽 偽 -diazoate with aromatic amines in aqueous solution was realized. Aniline, naphthylamine and tetrahydroindoles containing a variety of substituents were all suitable for the reaction, with the highest yield of 96.In addition, by regulating the size of cyclodextrin cavity, the ratio of aniline to diazoacetate N-H bond insertion product and double N-H bond insertion product can be adjusted to a certain extent.Formation of Sulphur and its Doyle-Kirmse reaction catalyzed by Hemin cyclodextrin-Traetone X-100 system in Aqueous Phase: blood Chloride was achieved by introducing Surfactant Traetone X-100 into the previous heme Cyclodextrin systemDiazo compounds and allyl sulfides are catalysed in aqueous phase by bilirubin to produce sulfurylides.Further Doyle-Kirmse rearrangement reaction occurred.The reaction conditions of the catalyst system are mild, with excellent substrate universality and good reaction yield. It is suitable for both aryl allyl sulfide and alkyl allyl sulfide which are insoluble.Heme-catalyzed [1z2] -Stevens and Sommelet-Hauser rearrangement of sulfoylides and their substrate-controlled chemical selectivity: through the control of the electron effect of substituents on benzyl sulfides and the selection of solvents,The benzyl thioylide produced by heme carbene has been selectively rearranged in [1t2] -Stevens reaction and Sommelet-Hauser rearrangement reaction. The [1t2] -Stevens reaction is easy to occur when the electron group or the benzyl sulfide substituted by the weak electron group is given.On the other hand, benzyl sulfides substituted by p-potential strong electron-absorbing groups are more likely to react with Sommelet-Hauser, and the Sommelet-Hauser reaction can be promoted by aqueous solution and proper lowering of temperature.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.251

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 Shou-Fei Zhu;Qi-Lin Zhou;;Iron-catalyzed transformations of diazo compounds[J];National Science Review;2014年04期

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本文編號(hào)：1763655