本文選題：Henry反應(yīng) + 不對(duì)稱催化��； 參考：《河北大學(xué)》2014年碩士論文

【摘要】：手性化合物對(duì)于化學(xué)和醫(yī)學(xué)具有非常重要的意義。獲得單一手性化合物的方法有很多，比如：手性拆分、自然界中提取、不催對(duì)稱合成等。從工業(yè)生產(chǎn)的角度來看，其中不對(duì)稱催化反應(yīng)作為獲得光學(xué)純化合物的一種手段在眾多方法中最具有原子經(jīng)濟(jì)性，同時(shí)也最具有挑戰(zhàn)性。催化不對(duì)稱Henry反應(yīng)是重要的構(gòu)筑碳碳鍵的方法。其β-硝基醇催化產(chǎn)物可以方便的轉(zhuǎn)化為相應(yīng)的手性醛、酮、羧酸、α-氨基醇等一系列有機(jī)合成的重要中間體。因此進(jìn)一步深入研究不對(duì)稱Henry反應(yīng)具有重要的理論意義和應(yīng)用前景。 根據(jù)文獻(xiàn)調(diào)研我們發(fā)現(xiàn)有三種類型的催化劑被應(yīng)用于不對(duì)稱Henry反應(yīng)中。其中包括：金屬配合物催化劑、有機(jī)小分子催化劑、季銨鹽類催化劑�；谇叭说墓ぷ�，我們以色氨酸為原料設(shè)計(jì)合成了一系列的新的催化劑并且把他們應(yīng)用于不對(duì)稱Henry反應(yīng)的研究中。 其主要內(nèi)容是： 以L-色氨酸為原料，合成了兩種不同類型的配體，并把它們與不同的金屬鹽配位后，研究其在催化醛與硝基烷烴的不對(duì)稱Henry反應(yīng)中的應(yīng)用。研究結(jié)果發(fā)現(xiàn)了一個(gè)高效的催化配體4a，在最優(yōu)條件下（-30oC，IPA為溶劑，100%DIPEA為添加劑，5%CuCl2.H2O為金屬鹽，），Cu(II)/4a配合物能高效地催化醛與硝基甲烷的反應(yīng)，并且對(duì)芳香醛、脂肪醛都有很好的選擇性，，ee值高達(dá)98%，以及99%的產(chǎn)率。在此基礎(chǔ)上我們還研究了Cu(II)/4a配合物催化醛與硝基乙烷的不對(duì)稱Henry反應(yīng)。研究結(jié)果表明，Cu(II)/4a配合物對(duì)于醛與硝基乙烷的反應(yīng)依然有很高的催化活性（產(chǎn)率99%），但是其對(duì)映選擇性效果卻不理想（dr=1：4.4； ee=30、23%）。同時(shí)，在我們把4a與金屬鹽絡(luò)合物應(yīng)用于(-)-denopamine中間體的合成中，取得了優(yōu)秀的效果，其產(chǎn)率達(dá)到了90%，ee值高達(dá)98%。 研究結(jié)果證明：我們所設(shè)計(jì)合成的新手性催化劑能高效、高對(duì)映選擇性地催化不對(duì)稱Henry反應(yīng)。催化劑合成簡便，成本低廉，用量低，金屬Cu鹽毒性低且對(duì)水空氣不敏感，相應(yīng)的催化產(chǎn)物具有很重要的實(shí)用價(jià)值。因此，該催化劑在工業(yè)領(lǐng)域具有很高的應(yīng)用前景，同時(shí)也為催化不對(duì)稱Henry反應(yīng)的研究提供了一條新的路徑。
[Abstract]:Chiral compounds are of great significance in chemistry and medicine. There are many methods to obtain single chiral compounds, such as chiral resolution, extraction from nature, asymmetric synthesis and so on. From the point of view of industrial production, asymmetric catalytic reaction as a means of obtaining optical pure compounds is the most atomic economy and the most challenging among many methods. Catalytic asymmetric Henry reaction is an important method to construct carbon and carbon bond. The catalytic products of 尾 -nitroalcohol can be easily converted into a series of important intermediates in organic synthesis, such as chiral aldehydes, ketones, carboxylic acids, 偽 -amino alcohols, etc. Therefore, the further study of asymmetric Henry reaction has important theoretical significance and application prospect. According to literature review, we found that three types of catalysts were used in asymmetric Henry reaction. These include: metal complex catalyst, organic small molecule catalyst, quaternary ammonium salt catalyst. Based on previous work, we designed and synthesized a series of new catalysts using tryptophan as raw material and applied them to the study of asymmetric Henry reaction. The main contents are as follows: two kinds of ligands were synthesized from L-tryptophan and coordinated with different metal salts to study their application in the asymmetric Henry reaction of aldehydes with nitroalkanes. It was found that a highly efficient catalytic ligand (4a) can efficiently catalyze the reaction of aldehydes with nitromethane under the optimum conditions (-30oCnIPA as solvent, 100DIPEA as additive, 5CuCl2.H2O as metal salt,) Cu (II) / 4a, and aromatic aldehydes. Aliphatic aldehydes have a high selectivity of 98% and yield of 99%. On this basis, we have also studied the asymmetric Henry reaction of aldehyde with nitroethane catalyzed by Cu (II) -4a complex. The results show that the cu (II) / 4a complex still has high catalytic activity (yield 99%) for the reaction of aldehyde with nitroethane, but its enantioselectivity effect is not ideal (drine 1: 4.4; Eee 30% 23%). At the same time, in the synthesis of (-) -denopamine intermediates with 4a and metal salts, excellent results have been obtained. The yield of 4a is up to 90% and the yield is as high as 98%. The results show that the new catalyst we designed and synthesized can catalyze asymmetric Henry reaction with high efficiency and high enantioselectivity. The synthesis of the catalyst is simple, low cost, low dosage, low toxicity of metal Cu salt and insensitive to water and air. The corresponding catalytic products have very important practical value. Therefore, the catalyst has a high application prospect in the industrial field, and also provides a new way for the study of asymmetric Henry reaction.
【學(xué)位授予單位】：河北大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：R914

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 蔡正艷;周偉澄;;立體選擇性還原的硼試劑及其在手性藥物合成中的應(yīng)用[J];有機(jī)化學(xué);2008年06期

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