【摘要】：含氮雜環(huán)化合物在農(nóng)藥、醫(yī)藥、材料以及其他精細(xì)化工領(lǐng)域中占有重要地位。探索綠色、經(jīng)濟(jì)、高效的合成方法,用以構(gòu)建含氮雜環(huán)化合物顯得尤為重要。1,3-偶極環(huán)加成反應(yīng)作為構(gòu)建雜環(huán)化合物的重要手段之一,也因此受到了越來(lái)越多的關(guān)注。本文發(fā)展了有機(jī)膦及金屬催化的原位生成的兩性離子與1,3-偶極子的環(huán)加成反應(yīng),構(gòu)建了一系列多元含氮雜環(huán)化合物,以期望篩選出農(nóng)藥新品種。本文發(fā)展了有機(jī)膦催化的酞嗪衍生的甲亞胺葉立德與聯(lián)烯酸酯的新型[3+2]環(huán)加成反應(yīng),在溫和的條件下,以91%-99%的產(chǎn)率構(gòu)建了一系列酞嗪并四氫吡咯類衍生物,此外還分別以88%產(chǎn)率得到異喹啉并四氫吡咯以及79%產(chǎn)率得到噠嗪并二氫吡咯類化合物,當(dāng)反應(yīng)擴(kuò)大至克級(jí)規(guī)模時(shí),仍然可以保持98%產(chǎn)率。此反應(yīng)豐富了有機(jī)膦催化領(lǐng)域的[3+2]環(huán)加成反應(yīng),為合成新型吡咯類雜環(huán)化合物提供借鑒參考。本文發(fā)展了首例手性膦催化的不對(duì)稱[4+3]環(huán)加成反應(yīng)。在Kwon手性膦催化下,聯(lián)烯酸酯與喹唑啉衍生的偶氮次甲基亞胺發(fā)生不對(duì)稱[4+3]環(huán)加成反應(yīng),可以高達(dá)98%產(chǎn)率,33:1 dr的非對(duì)映選擇性以及96%ee的對(duì)映選擇性得到喹唑啉并四氫二氮雜卓類化合物,此外,[4+3]環(huán)加成產(chǎn)物經(jīng)氧化開(kāi)環(huán),可在保持手性的情況下,以高產(chǎn)率得到了系列單環(huán)的四氫二氮雜卓類化合物。本文發(fā)展了銅催化1,3-偶極子對(duì)1,3-偶極子的不對(duì)稱[3+3]環(huán)加成反應(yīng)。在四氟化硼(四乙腈)銅與手性二茂鐵配體催化下,酞嗪衍生的甲亞胺葉立德與亞胺乙酸酯衍生的甲亞胺葉立德可以高達(dá)99%產(chǎn)率,20:1 dr的非對(duì)映選擇性以及99%ee的對(duì)映選擇性,構(gòu)建系列酞嗪并哌嗪類環(huán)狀化合物。此外,將反應(yīng)放大至克級(jí)規(guī)模時(shí),仍然可以保持95%產(chǎn)率,20:1 dr的非對(duì)映選擇性以及94%ee的對(duì)映選擇性。此反應(yīng)為手性哌嗪環(huán)的合成提供了新的方法依據(jù)。本文報(bào)道了鈀催化的乙烯基碳酸乙烯酯作為五元合成子與偶氮次甲基亞胺的[5+3]環(huán)加成反應(yīng),在溫和的反應(yīng)條件下,以高達(dá)98%產(chǎn)率以及99:1的化學(xué)選擇性,構(gòu)建了喹唑啉以及異喹啉并八元環(huán)狀化合物,發(fā)展了一鍋法合成中環(huán)化合物。
[Abstract]:Nitrogen heterocyclic compounds play an important role in pesticide, medicine, materials and other fine chemicals. It is very important to explore green, economical and efficient synthesis methods to construct nitrogen-containing heterocyclic compounds. As one of the important means of constructing heterocyclic compounds, it is becoming more and more important to construct nitrogen-containing heterocyclic compounds. In this paper, a series of heterocyclic compounds containing nitrogen were constructed by the cycloaddition reaction of organophosphine and metal-catalyzed in situ amphoteric ions with 1 ~ (3) -dipole, in order to screen out new pesticide varieties. In this paper, a new [32] cycloaddition reaction of dienoate with metimide ylide derived from phthalazine catalyzed by organic phosphine was developed. Under mild conditions, a series of phthalazine and tetrahydropyrrole derivatives were constructed in a yield of 91- 99%. In addition, isoquinoline tetrahydropyrrole and pyridazinopyrrole compounds were obtained in 88% yield and 79% yield, respectively. The yield of pyridazinopyrrole compounds remained 98% when the reaction was extended to gram order. This reaction enriches the [32] cycloaddition reaction in the field of organic phosphine catalysis and provides a reference for the synthesis of new pyrrole heterocyclic compounds. The first asymmetric [43] cycloaddition reaction catalyzed by chiral phosphine has been developed. Under the catalysis of Kwon chiral phosphine, [43] cycloaddition reaction of [43] cycloaddition of azomethimide derived from quinazoline was observed. The enantioselectivity of 33: 1 dr and 96% enantioselectivity of quinazoline and tetrahydrodiazepines can be obtained by up to 98% yield. In addition, the [43] cycloaddition product can be oxidized and the chiral property can be maintained. A series of monocyclic tetrahydrodiazepines were obtained in high yield. In this paper, the asymmetric [33] cycloaddition reaction of 1 ~ (3) -dipole catalyzed by copper has been developed. Under the catalysis of copper tetrafluoride (tetraacetonitrile) and chiral ferrocene ligands, the enantioselectivity and enantioselectivity of methyl imine ylide derived from phthalazine and imine acetate can reach up to 99%, 20: 1 dr and 99%, respectively. A series of phthalazine and piperazine ring compounds were constructed. In addition, the enantioselectivity of 95% yield of 20: 1 dr and 94% of enantioselectivity can be maintained when the reaction is enlarged to g order. This reaction provides a new method for the synthesis of chiral piperazine ring. The palladium catalyzed [53] cycloaddition reaction of vinylidene carbonate with azomethimide as a quaternary synthesizer was reported in this paper. Under mild reaction conditions, the yield of vinyl carbonate was as high as 98% and the chemical selectivity of 99:1 was obtained. Quinazoline and isoquinoline octa-ring compounds were synthesized by one-pot method.
【學(xué)位授予單位】：中國(guó)農(nóng)業(yè)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2條

1 張芝平;吡咯類殺蟲(chóng)劑的構(gòu)效關(guān)系和作用機(jī)理研究[J];世界農(nóng)藥;1999年06期

2 屠豫欽;天然源農(nóng)藥的研究利用—機(jī)遇與問(wèn)題[J];世界農(nóng)藥;1999年04期

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本文編號(hào)：2216613