Probe for bio-oligomers and elucidation of their function

本研究完成了多功能化生物寡聚体的衍生化和新功能的开发，并沿着以2，6-二甲基苯酯的Fries反应为关键反应，实现了激光解吸电离质谱（LDI-MS）用光裂解分子标记物的合成。发现氯化锆是促进反应的唯一有效的助剂。该分子标签经5步反应制得，无需层析纯化，并建立了叔胺存在下羟基的苄基化反应。在二异丙基乙胺存在下，醇和苄基卤的混合物以良好至优异的产率提供相应的苄基醚。观察到无溶剂条件的重要性。该反应显示出对包括苯甲酸酯在内的许多官能团的高耐受性，甚至在150°C的反应温度下。碘化钠被发现是一种有效的催化剂，以加速反应。该操作简单，可成功应用于LDI-MS分析的前处理，并通过缩酮反应合成了以1，2-二醇基序为靶点的新型糖捕获剂。设计并合成了带有α二酮功能的光切割分子标签。由于该化合物不具有冗余的系链亚结构，因此高灵敏度与先前制备的化合物相当。

General procedures for derivatization of multi functionalized bio-oligomers and exploitation of new function to capture a target molecules connecting photocleavable molecular tag were achieved in this research.Along with the experiment, a new synthetic route for the photocleavable molecular tag for laser desorption ionization mass spectrometry(LDI-MS) was achieved using Fries reaction of 2, 6-dimethylphenyl ester as its key reaction. Zirconium chloride was found as uniquely efficient adjuvant to promote the reaction. The molecular tag was obtained in 5 steps without chromatographic purification.And, the Benzylation of hydroxyl groups in the presence of tertiary amines is established. A mixture of an alcohol and a benzyl halide afforded the corresponding benzyl ether in good to excellent yields in the presence of diisopropylethylamine. The importance of solventless conditions was observed. The reaction showed high tolerance to many functional groups including benzoate, even at a reaction temperature of 150°C. Sodium iodide was found to be an efficient catalyst to accelerate the reaction. The simple operation was successfully applied for pre-treatment of LDI-MS analysis.Then, new trapping agent for sugars targeting 1, 2-diol motif by mean of ketal formation reaction. Photocleavable molecular tag bearing alpha diketone functioality was designed and synthesized. Since the compound does not have redundant tether substructure, high sensitivity is comparable with compounds previously prepared.