發(fā)布時間：2018-02-03 03:15

  本文關(guān)鍵詞： 環(huán)加成反應(yīng) 不對稱催化 亞甲胺葉立德 環(huán)丙烷 氮雜環(huán)丙烷 氰基亞胺　出處：《中國農(nóng)業(yè)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：1,3-偶極環(huán)加成反應(yīng)是一種合成雜環(huán)化合物的重要方法,已廣泛應(yīng)用于天然產(chǎn)物和具有生物活性分子的合成。路易斯酸作用下原位生成的亞甲胺葉立德、路易斯酸催化下環(huán)丙烷和氮雜環(huán)丙烷開環(huán)形成的1,3-偶極子及在堿的作用下原位生成的氰基亞胺作為常用的原位生成的1,3-偶極子都可以參與1,3-偶極環(huán)加成反應(yīng),基于這些偶極子開發(fā)的[3+2]環(huán)加成反應(yīng)已有大量報道,而其他形式的環(huán)加成反應(yīng)則相對較少。在這種背景下,本文旨在發(fā)展基于這些偶極子的新型環(huán)加成反應(yīng),例如[3 + 3]、[6 + 3]、[8+ 3]及雙[3 + 2]環(huán)加成反應(yīng),合成多樣性的雜環(huán)化合物�；诼芬姿顾岽呋膩喖装啡~立德與貧電烯及富烯的環(huán)加成反應(yīng),本文首先發(fā)展了銅鹽和二茂鐵膦氮手性配體形成的催化劑催化的α-亞胺酯與N,N'-環(huán)狀偶氮次甲基亞胺的不對稱[3 + 3]環(huán)加成反應(yīng),該反應(yīng)適用于各種芳香取代的底物,可以在溫和的反應(yīng)條件下進行,原料簡單易得,可以高收率、高非對映選擇性和高對映選擇性地得到環(huán)加成產(chǎn)物。產(chǎn)物在酸性條件下可以進行差向異構(gòu)化,在硼氫化鋰的作用下可以通過擴環(huán)得到含氮和氧的八元環(huán)產(chǎn)物。之后我們發(fā)展了金屬催化的亞甲胺葉立德與環(huán)庚三烯酮的[6 + 3]環(huán)加成反應(yīng),通過銀鹽和三苯基膦的絡(luò)合物作為催化劑實現(xiàn)了其消旋催化,通過使用銅鹽和二茂鐵膦氮手性配體的絡(luò)合物作為手性催化劑,發(fā)展了高對映選擇性催化反應(yīng)。該反應(yīng)原料易得,條件溫和,可以放大量到克級,產(chǎn)物可以在鈀碳加氫還原的條件下得到碳碳雙鍵還原的產(chǎn)物,在硼氫化鈉的還原條件下得到羰基還原成羥基的產(chǎn)物,證明該反應(yīng)有很好的實用性�；诼芬姿顾峥梢曰罨h(huán)丙烷和氮雜環(huán)丙烷開環(huán)形成1,3-偶極子從而進行環(huán)加成反應(yīng),本文發(fā)展了三氟甲磺酸鈧催化的1,1-雙酯基環(huán)丙烷與酞嗪衍生的雙氰基葉立德的[3 + 3]環(huán)加成反應(yīng),該反應(yīng)可以高收率得到單一的非對映異構(gòu)體,底物范圍廣,并可放大量到克級,產(chǎn)物在鈀碳還原的條件下能得到一個氰基還原成胺的產(chǎn)物,在硼氫化鈉的甲醇溶液中能將產(chǎn)物中一個氰基轉(zhuǎn)換成一個甲氧基。其后本文發(fā)展了高氯酸鎳催化的氮雜環(huán)丙烷與環(huán)庚三烯酮的[8 + 3]環(huán)加成反應(yīng)。該反應(yīng)可放大到克級,產(chǎn)物可以在鈀碳還原加氫的條件下進行碳碳雙鍵還原衍生化。本文還發(fā)展了氰基亞胺與聯(lián)烯酯的連續(xù)[3 + 2]環(huán)加成反應(yīng),該反應(yīng)通過一鍋法反應(yīng),高收率、高非對映選擇性地合成了雙吡唑啉螺環(huán)化合物,實現(xiàn)了同時構(gòu)造螺環(huán)的兩個五元環(huán),并適用于各種取代的氰基亞胺前體和α-取代聯(lián)烯酯。
[Abstract]:As an important method for the synthesis of heterocyclic compounds, 1H _ 3- dipolar cycloaddition reaction has been widely used in the synthesis of natural products and bioactive molecules. Under the catalysis of Lewis acid, 1 / 3- dipole formed by ring opening of cyclopropane and azacyclopropane and cyanoimide in situ formed under the action of alkaloids can be involved as 1 / 3- dipole, which is commonly used for in situ generation of cyclopropane and azacyclopropane. 3-dipole cycloaddition reactions, based on the. [32] Cycloaddition reactions have been widely reported, while other forms of cycloaddition reactions have been relatively few. In this context, this paper aims to develop new cycloaddition reactions based on these dipoles, such as. [3 3], [6 3], [8 3 / 2. [3 2] cycloaddition reaction to synthesize heterocyclic compounds. Cyclization reaction of methylamine ylide with allene and fulene catalyzed by Lewis acid. In this paper, the catalysts for the chiral ligand formation of copper salt and ferrocene phosphine nitrogen have been developed. The asymmetric properties of 偽 -imide and N- Na-cyclic azomethyl imine catalyzed by copper salt and ferrocene phosphine nitrogen chiral ligands have been developed. [3] cycloaddition reaction, which is suitable for various aromatic substituted substrates, can be carried out under mild reaction conditions, the raw material is simple and easy to obtain, and the yield is high. The cycloaddition products were obtained by high enantioselectivity and high enantioselectivity. Under the action of lithium borohydride, the octa-ring products containing nitrogen and oxygen can be obtained by ring expansion. After that, we have developed metal-catalyzed methylamine ylide and cycloheptylenone. [The complex of silver salt and triphenylphosphine was used as catalyst for racemic catalysis, and the complex of copper salt and ferrocene phosphine nitrogen chiral ligand was used as chiral catalyst. The high enantioselective catalytic reaction was developed. The raw material is easy to be obtained and the conditions are mild. The product can be released to g level and the product can be reduced by carbon and carbon double bond under the condition of palladium carbon hydrogenation. Under the condition of reduction of sodium borohydride, carbonyl group was reduced to hydroxyl group, which proved that this reaction is very practical. Based on Lewis acid, ring opening of cyclopropane and azacyclic propane can be formed. The cycloaddition reaction of 3-dipole was carried out. In this paper, the dicyanoylide derived from 1-diester cyclopropane and phthalazine catalyzed by scandium trifluoromethyl sulfonate was developed. [3] Cycloaddition reaction, this reaction can obtain a single enantiomer in high yield, with a wide range of substrates, and can be put up to the gram level. Under the condition of palladium carbon reduction, a cyanide can be reduced to amine. In methanol solution of sodium borohydride, one cyanide group in the product can be converted into a methoxy group. Subsequently, the catalytic properties of heterocyclic propane and cycloheptylenone catalyzed by nickel perchlorate have been developed. [8 3] cycloaddition reaction. The reaction can be amplified to g order, and the product can be deoxidized by carbon and carbon double bond derivatization under the condition of palladium carbon reduction and hydrogenation. The continuous reaction of cyanoimide and dienyl ester has also been developed. [32] cycloaddition reaction, which synthesized bispyrazoline spirocyclic compounds with high yield and high enantioselectivity by one-pot reaction, and realized the simultaneous construction of two five-member rings of snails. It is suitable for all kinds of substituted cyanoimide precursors and 偽-substituted dienyl esters.
【學(xué)位授予單位】：中國農(nóng)業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O621.251

【參考文獻】

相關(guān)期刊論文 前1條

1 白國義,陳立功,李陽,曹琳,宋傳君,王豐雷;1,3-偶極環(huán)加成反應(yīng)在他唑巴坦合成中的應(yīng)用[J];天津大學(xué)學(xué)報;2002年03期

，

本文編號：1486257