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N-甲基吡哆醛催化甘氨酸肽對亞胺的不對稱加成

發(fā)布時(shí)間:2018-03-07 05:11

  本文選題:N-甲基吡哆醛 切入點(diǎn):α 出處:《上海師范大學(xué)》2017年碩士論文 論文類型:學(xué)位論文


【摘要】:α,β-二氨基酸及其衍生物以其較好的生物活性在醫(yī)藥及生物化學(xué)方向上都有廣泛應(yīng)用。雖然合成α,β-二氨基酸及其衍生物的方法已經(jīng)報(bào)道了很多,但是發(fā)展更高效、環(huán)境友好的α,β-二氨基酸及其衍生物的合成方法仍然極具挑戰(zhàn)性。在生物體內(nèi),溫和的條件下甘氨酸可以在基于aldol酶的維生素B6催化下直接對醛進(jìn)行aldol加成得到β-羥基α-氨基酸。受此啟發(fā),我們發(fā)展了一系列手性N-甲基吡哆醛催化劑,并且成功將其用于催化甘氨酸二肽對亞胺的不對稱Mannich加成反應(yīng),從而得到各種α,β-二氨基酸二肽衍生物。該反應(yīng)有很好的收率和ee值,并且具有一定得非對映選擇性。本文的主要工作包括一下四個(gè)方面:(1)設(shè)計(jì)并發(fā)展了一系列具有不同側(cè)鏈的軸手性聯(lián)芳骨架N-甲基吡哆醛催化劑,并成功實(shí)現(xiàn)了該類催化劑催化甘氨酸二肽對亞胺的不對稱加成反應(yīng)。(2)使用最佳催化劑對該反應(yīng)進(jìn)行條件優(yōu)化,其中包括對溶劑、溶劑與水的比例、溫度、添加劑種類及其當(dāng)量、底物濃度及其當(dāng)量比、甘氨酸肽底物等進(jìn)行了篩選。(3)在最優(yōu)反應(yīng)條件下對亞胺進(jìn)行了底物拓展得到一系列不同的α,β-二氨基酸二肽衍生物,其中反應(yīng)收率在48%-91%之間,主產(chǎn)物ee值高達(dá)99%。(4)對N-甲基吡哆醛催化甘氨酸二肽對亞胺的不對稱Mannich加成反應(yīng)提出可能的反應(yīng)機(jī)理。
[Abstract]:偽, 尾 -diamino acids and their derivatives have been widely used in medicine and biochemistry because of their good biological activities. Although many methods of synthesizing 偽, 尾 -diamino acids and their derivatives have been reported, they have been developed more efficiently. The synthesis of environmentally friendly 偽, 尾 -diamino acids and their derivatives remains extremely challenging. A series of chiral N-methylpyridoxal catalysts were developed under mild conditions in which glycine can be directly added to aldehydes by aldol addition under the catalysis of vitamin B _ 6 based on aldol enzyme, so we have developed a series of chiral N-methylpyridoxal catalysts. It has been successfully used to catalyze the asymmetric Mannich addition reaction of glycine dipeptide to imine and to obtain various 偽, 尾 -diamino acid dipeptide derivatives. The main work of this paper includes four aspects: design and development of a series of chiral N-methylpyridoxal catalysts with different side chains. The asymmetric addition reaction of glycine dipeptide to imine catalyzed by this kind of catalyst was successfully realized. The optimum catalyst was used to optimize the reaction conditions, including solvent, solvent to water ratio, temperature, additive type and its equivalent. A series of 偽, 尾 -diamino acid dipeptide derivatives were obtained under the optimum reaction conditions by screening the substrate concentration and its equivalent ratio, glycine peptide substrate and so on. The yield of the reaction was between 48% and 91%. The EE value of the main product was as high as 99 / 4). The possible mechanism of the asymmetric Mannich addition of glycine dipeptide to imine catalyzed by N-methylpyridoxal was suggested.
【學(xué)位授予單位】:上海師范大學(xué)
【學(xué)位級別】:碩士
【學(xué)位授予年份】:2017
【分類號】:O621.251

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