新型手性咪唑鎓环番的合成及对氨基酸的对映选择性识别  

Design and Synthesis of Novel Chiral Imidazolium Cyclophanes and Their Enantioselective Recognition for α-Amino Acids and Their Derivatives

作　　者：郭生金[1] 罗奎[1] 王文海[1] 张仕勇[1] 蒋和雁[1] 兰静波[1] 谢如刚[1] 

机构地区：[1]四川大学化学系

出　　处：《高等学校化学学报》2006年第9期1664-1668,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20472057;20574046);教育部博士学科点专项基金(批准号:20040610011)资助

摘　　要：以L-氨基酸为手性源，合成了一系列新型手性咪唑鎓环番，并进行了结构表征．在碱性条件下，L-氨基酸和乙二醛、甲醛缩合生成了（S）-2-（1-咪唑）羧酸钠，转化为甲酯后与乙二胺进行胺解反应制得开链手性咪唑二酰胺，然后与二溴化合物在高稀淡技术和无水条件下进行季铵化关环反应，再进行阴离子交换制得目标分子（4—6）．以手性咪唑鎓环番为主体分子，研究了对氨基酸及其衍生物的对映选择性识别作用．A series of novel chiral imidazolium cyclophanes were synthesized from natural amino acids. （S）-2-（ 1-Imidazolyl） alkanoates （2） were prepared by cyclization and esterification. In the presence of DMAP and Et3N. Alkanoates（2） reacted with ethylenediamine to yield compounds 3 with satisfactory yields. Compounds 3 reacted with 2,6-bis（bromomethyl） - 4-chlorphenol, 1,3-bis（bromomethyl） benzene or 2,6-bis（ bromomethyl） pyridine to afford dibromide salts under high dilution and anhydrous condition. Finally, the hexafluorophosphates （4-6） were obtained by treating the corresponding dibromide salts with a saturated aqueous solution of NH4 PF6. The structures of the target compounds were confirmed by IR, ^1 H NMR, MS, HRMS, and elemental analysis. These compounds featured large cavities and multipoint binding sites. UV spectroscopic titration experiments showed these chiral imidazolium cyclophanes exhibited good enantioselective recognition toward L- and D-amino acids and their derivatives.

关 键 词：氨基酸 手性咪唑鎓环番 合成 对映选择性识别 

分 类 号：O626.23[理学—有机化学] O614[理学—化学]