吡哆醛催化酮酸转氨化的研究

【作者】 陈静；

【导师】 赵宝国； 许东芳；

【作者基本信息】 上海师范大学 ， 高分子化学与物理， 2015， 硕士

【摘要】 氨基酸是一类非常重要的有机化合物,在食品、药物和化工等领域中都有着重要的应用。转氨化是生物体合成氨基酸最重要的途径。由于的酶价格昂贵,底物适用范围窄等缺点,不利于工业生产和有机合成的应用。因此,生物模拟α-酮酸转氨化的研究有重要意义,为氨基酸的合成提供了新方法。吡哆醛及其衍生物是酶催化转氨化的活性中心,在酶催化的转氨化过程中,涉及到碱去质子化和酸质子化的过程,因此,我们在吡哆醛分子上合适的位置引入适当的碱或/和酸的基团,合成了一系列的吡哆醛催化剂,并考察了它们在α-酮酸转氨化反应中的催化性能,筛选出活性较高的催化体系。通过转氨化的方法,合成了一系列的α-氨基酸。该反应条件温和,易于操作,重复性好。更多还原

【Abstract】 Amino acid is a kind of very important organic compounds with extensive applications in many areas including food science, medicinal chemistry and chemical industry. Enzymatic transamination of α-keto acids plays an important role in the synthesis of α-amino acids in biological system. Due to high price of transaminases and limited substrate scope, enzymatic transamination has little application for the synthesis of α-amino acids in organic chemistry and organic labs. Biomimetic transamination by using chiral pyridoxal and its derivatives as catalyst provides a new and attractive strategy for the synthesis of α-amino acids. The studies are not only theoretically important, but also have a practical potential.Pyridoxal and its derivatives are the catalysis center in enzymatic transamination. It has been proposed that deprotonation with base and protonation with acid occur during the catalytic cycle of enzymatic transamination. The participation of base and/or acid facilitates the transamination by lowering the activation energy of the reaction. Thus, introducing appropriate functional groups such as amine, acid, urea and so on onto pyridoxal might form more active catalysts for biomimetic transamination.In this thesis, we designed and synthesized a series of pyridoxals tagged with different functional groups. The pyridoxals exhibited high catalytic activity in transamination of α-keto acids, proving various amino acids in good yields. The transformation with some obvious advantages such as mild reaction conditions and easy operation represents a potentially practical method for the synthesis of α-amino acids.更多还原