【作者】 赵志刚；

【导师】 陈淑华；

【作者基本信息】 四川大学 ， 有机化学， 2006， 博士

【摘要】 分子识别是生物体系的基本的特征,并在生命活动中起中心作用。利用人工受体建立化学模型或化学仿生体系来研究生物体内的分子识别现象已经成为生物有机化学和超分子化学前沿富于挑战性的课题之一。在众多人工受体模型中,分子钳作为一类新型的人工受体已引起人们的广泛关注。本文致力于鹅去氧胆酸,α–猪去氧胆酸和脱氧胆酸类分子钳人工受体的设计合成及其对阴离子、中性分子、手性分子的识别与手性识别研究,取得了一系列具有重要学术意义和应用前景的创新性结果。以鹅去氧胆酸,α–猪去氧胆酸和脱氧胆酸作为隔离基,设计合成了酯键型、氨基甲酸酯型、不对称脲型三大类六个系列,共计65个分子钳人工受体,其中55个是未见文献报道的新化合物。鹅去氧胆酸分子钳、氨基甲酸酯型α–猪去氧胆酸分子钳和脱氧胆酸–不对称脲分子钳为全新设计和首次合成。深入地研究了目标物的合成方法,优化了反应条件,实现了多种简便有效的合成目标物的方法。首次运用微波法对酯键型α–猪去氧胆酸分子钳的合成进行了研究,探索了一系列反应条件诸如微波功率、辐射时间、溶剂的种类等对反应的影响,成功地以80%以上的产率合成了目标物。在氨基甲酸酯型α–猪去氧胆酸和脱氧胆酸分子钳的合成中,采用微波法,以三光气代替剧毒的光气,采取分步加料一锅合成法,以90%以上的产率成功地合成了26个目标化合物。实现了一条简便、安全、高产率的合成氨基甲酸酯型胆甾化合物的新方法。微波法显著的缩短了反应时间,提高了产率,实现了一种对环境友好的、具有绿色化更多还原

【Abstract】 Molecular recognition is a fundamental characteristic of biochemical systems and plays a central role in biological processes. The study on molecular recognition using the artificial receptors to construct the chemical models or biomimetic systems is one of the challenges in the frontiers of bioorganic chemistry and supramolecular chemistry. Among the variety of artificial receptor models, a special class of receptors called molecular tweezer are currently attracting great interest. In this dissertation, the efforts were focused on design and synthesis of molecular tweezers derived from chenodeoxycholic acid,α–hyodeoxycholic acid and deoxycholic acid and their molecular recognition as well as enantioselective recognition for anions, neutral molecules and chiral molecules. A series of useful, important and creative results have been obtained.Six series of molecular tweezers based on chenodeoxycholic acid,α–hyodeoxycholic acid and deoxycholic acid, including ester-bond type, carbaminate type and unsymmetrical urea, have been designed and synthesized. Fifty five compounds of sixty five molecular tweezers are new compounds. Chenodeoxycholic acid, carbaminate typeα–hyodeoxycholic and deoxycholic acid unsymmetrical urea molecular tweezers were designed and synthesized for the first time. The synthetic methods of the target compounds have been systematically investigated. The更多还原