【作者】 喻琳；

【导师】 赵玉芬；

【作者基本信息】 厦门大学 ， 有机化学， 2005， 硕士

【摘要】 氨基酸五配位磷化合物在有机磷化学和生物化学中具有重要的作用。氨基酸被磷酰后,可以在水/醇体系中发生一系列仿生化反应,如成肽反应、成酯反应、酯交换反应和磷上的N O迁移等,这些生物有机反应均经历氨基酸磷烷中间体。氨基酸成肽反应是生命起源中一个重要的反应。这样N-磷酰化氨基酸的成肽反应就成了“蛋白与核酸共起源”模型的重要组成部分。因此,合成稳定的氨基酸磷烷,并研究其性质以及成肽反应,不仅对于揭示蛋白质的生物合成和生命起源具有重要理论意义,而且对多肽合成也具有实用价值。本论文运用了核磁共振、电喷雾质谱、X射线衍射、分子模拟等分析手段,对一系列五配位氨基酸氢膦烷的合成,物理和化学性质,以及对酪氨酸酶的抑制活性和机理进行了探讨,主要成果如下:以氨基酸为原料合成了一系列单分子和双分子氨基酸氢膦烷。产物用31P、1H以及质谱进行了表征。合成路线具有条件温和、快速、易于操作和产率较高等特点。利用磷谱对氨基酸氢膦烷的合成过程进行了跟踪研究,初步探讨了反应机理。同时还发现只有α-氨基酸才能形成氨基酸氢膦烷,β-氨基酸则不能。通过实验证明,较双氨基酸氢磷烷而言,单分子氨基酸氢膦烷化学性质较为活泼,易水解;而双氨基酸氢膦烷反应活性与一些以往的五配位磷化合物不同,较为稳定,反应活性较弱,不易发生水解,甚至在酸、碱条件下也不易水解。磷谱表明,氨基酸氢膦烷通常是以一对非对映异构体在溶液中存在的。通过重结晶的方法得到双丙氨酸氢磷烷的单晶,并对其进行了X-射线单晶结构测定。结果表明,磷与五个配位原子形成稍稍扭曲更多还原

【Abstract】 Pentacoordinated spirophosphoranes derived from amio acids are very important in organic phosphorus chemistry and biological chemistry. N-phospho-α-amio acids are obtained by phospholation of amio acids, and they can take place many kinds of bioorganic reactions in water/alcohol media. For example, peptide formation, the ester formation, the ester exchange on phosphorus and N O phosphoryl migration reactions are observed. The synthesis of peptide is one of the most crucial reactions in origin of life. And then the peptide formation from N-phospho-α-amio acids plays a significant role in the model of the coevolution of protein and nucleotides. Hence, it is very important to study the synthesis and reactivity of the pentacoordinated spirophosphoranes containing amino acid moiety. To obtain the unambiguous structure characterization is not only important for comprehending the biosynthesis of proteins but also for the study origin of life.In this thesis, the synthesis, physic and chemical characters, the bioactivity and the reaction mechanism were studied with assistance of NMR, ESI-MS, X-ray diffraction and theoretical chemistry technology. The results are illustrated as following:Two types of amino acid spirophosphoranes were synthesized. The products were characterized by using many kinds of technology. The method is very simple and convenient with reasonable yield. To study the mechanism, the reaction was traced by 31P NMR spectroscopy. It was found that onlyα-amino acids could be converted into spirophosphoranes更多还原