本文關(guān)鍵詞：金催化的串聯(lián)反應(yīng)于雜環(huán)化合物的合成　出處：《山東大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： Au催化 一鍋法 串聯(lián)反應(yīng) 嗎啡啉 含氮橋環(huán)化合物

【摘要】：近幾年來,金催化劑已經(jīng)引起了科學(xué)家們的廣泛關(guān)注。金催化的反應(yīng)通常具有反應(yīng)活性高、化學(xué)選擇性強、反應(yīng)條件溫和且對空氣和水并不敏感等一系列優(yōu)點,因此被廣泛應(yīng)用于各種有機合成和天然產(chǎn)物的全合成中。金催化劑參與的反應(yīng)主要集中于對不飽和鍵(尤其是炔烴)的活化從而實現(xiàn)的親核加成反應(yīng),另外還有對碳氫鍵的活化反應(yīng)和少數(shù)氧化還原反應(yīng)等。本論文利用了金催化劑優(yōu)異的催化性質(zhì),設(shè)計了兩類金催化劑參與的串聯(lián)反應(yīng),實現(xiàn)了兩種雜環(huán)化合物的一鍋法高效合成。論文主要包含兩部分內(nèi)容:多取代嗎啡啉衍生物的合成以及復(fù)雜氮橋環(huán)化合物的合成。論文的第一部分中,我們以氮雜環(huán)丙烷和炔丙醇作為起始底物,高效地得到了多取代的嗎啡啉衍生物。首先,氮雜環(huán)丙烷在Au(Ⅰ)作用下與炔丙醇發(fā)生一步開環(huán)親核加成反應(yīng)得到炔酰胺中間體,之后金催化劑活化三鍵,發(fā)生分子內(nèi)環(huán)化氫胺化反應(yīng)生成環(huán)外烯胺中間體,該中間體迅速異構(gòu)成更穩(wěn)定的環(huán)內(nèi)烯胺結(jié)構(gòu)。在該串聯(lián)反應(yīng)進程中,金催化劑同時以lewis酸和π酸兩個身份參與了反應(yīng),以分別活化氮雜環(huán)丙烷和碳碳三鍵。之后利用Pd/C催化加氫反應(yīng)便可以極高的產(chǎn)率和dr值高效地得到目標(biāo)產(chǎn)物。我們還獲得了最終產(chǎn)物的單晶結(jié)構(gòu),從而確定了該產(chǎn)物中取代基團的相對構(gòu)型。論文的第二部分中,我們以含苯環(huán)的炔酰胺類化合物和各種親雙烯體作為原料,成功合成了一類復(fù)雜的含氮橋環(huán)化合物。在這份工作中,首先由金催化劑催化炔酰胺類化合物發(fā)生分子內(nèi)環(huán)化氫胺化得到苯并五元環(huán)外烯胺中間體,此時該中間體并未被另一反應(yīng)物所捕獲,而是在生成后迅速發(fā)生了[1,5]-氫遷移反應(yīng)從而構(gòu)筑了取代的異吲哚中間體,之后該中間體與一分子親雙烯體原料發(fā)生Diels-Alder環(huán)加成反應(yīng)從而生成目標(biāo)產(chǎn)物。我們采用一鍋法在單一金催化劑的作用下實現(xiàn)了三步有序的串聯(lián)反應(yīng),且在很短的反應(yīng)時間內(nèi)以十分溫和的條件引發(fā)了[1,5]-氫遷移反應(yīng)。我們還做了一系列的氘代實驗來研究反應(yīng)機理,從而證明了[1,5]-氫遷移反應(yīng)歷程的存在,進一步證實了我們對反應(yīng)機理的推測。同時我們也拿到了產(chǎn)物的單晶結(jié)構(gòu),佐證了我們的反應(yīng)結(jié)果。
[Abstract]:In recent years, gold catalysts have attracted wide attention of scientists. Gold catalytic reactions usually have a series of advantages such as high reaction activity, strong chemical selectivity, mild reaction conditions and insensitivity to air and water. Gold catalysts are mainly involved in the activation of unsaturated bonds (especially alkynes) to achieve nucleophilic addition. In addition, there are the activation of hydrocarbon bonds and a few redox reactions. In this paper, two kinds of gold catalysts are designed to participate in series reactions using the excellent catalytic properties of gold catalysts. One-pot synthesis of two heterocyclic compounds has been realized. The thesis mainly includes two parts: the synthesis of polysubstituted morphine derivatives and the synthesis of complex nitrogen bridged ring compounds. In the first part of the thesis. We used azacyclic propane and propargyl alcohol as starting substrates to efficiently obtain polysubstituted morphine derivatives. The nucleophilic addition reaction of azacyclic propane with propargyl alcohol was carried out in one step under the action of au (I) to obtain the intermediate of acetylidene, and then the gold catalyst activated three bonds. The intramolecular cyclized hydroamination reaction produces an extracyclic enamine intermediate, which rapidly dissolves to form a more stable cyclienamine structure, and in the process of the series reaction. Gold catalyst participated in the reaction as lewis acid and 蟺 acid simultaneously. The target product can be obtained efficiently by Pd/C catalytic hydrogenation with the activation of heterocyclic propane and carbon tribond respectively. The single crystal structure of the final product is also obtained. In the second part of this paper, we use benzene-ring acetylene amides and dienophiles as raw materials. A class of complex nitrogen-containing bridged ring compounds was successfully synthesized. In this work, the intermediates of benzo-pentacyclic enylamine were synthesized by intramolecular cyclization of alkyne amines catalyzed by gold catalysts. At this point, the intermediate is not captured by another reactant, but occurs quickly after its formation. [The substituted isoindole intermediates were constructed by hydrogen migration reaction. Then the intermediate reacts with a molecular dienophile by Diels-Alder cycloaddition reaction to produce the target product. We have realized a three-step ordered series by one-pot method under the action of a single gold catalyst. Combined reaction. And in a very short reaction time, under very mild conditions, [We have also done a series of deuteration experiments to study the mechanism of the reaction. [The existence of 1 / 5] -hydrogen migration mechanism further confirmed our speculation of the reaction mechanism. At the same time, we also obtained the single crystal structure of the product, which confirmed our reaction results.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O626
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本文編號：1371357