Synthesis of chiral calixarenes and application as functional organic catalysts

手性杯芳烃的合成及其作为功能有机催化剂的应用

• 批准号: 17560685
• 负责人: GOTO Koichi
• 金额: $ 2.05万
• 依托单位: Sojo University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17560685/
• 关键词: Chiral Calixarene; Amino Acid Ester; Enantioselective Hydrolysis; Molecular Recognition; Supramolecular Chemistry; 触媒・化学プロセス; カリックスアレーン; キラリティー; 不斉触媒; エステル化反応; アミノ酸

The racemic mixture of chiral calix [4]arenes (5-tert-butyl-11-methyl-17,23-diphenyl-25,26,27,28-tetrahydroxycalix [4]arene) with three different upper rim substituents was synthesized by the fragmentation-condensation of p-substituted phenol dimmers (2-(5-methylsalicyl)-4-tert-butylphenol and 3-(3-hydroxymethyl-5-phenylsalicyl)-5-phenyl-2-hydroxybenzyl alchol) according to K. No and coworkers' multi-step method. On the other hand, amino acid esters (Z-D(L)-Ala-PNP, Z-D(L)-Trp-PNP) were prepared from N-(benzyloxycarbonyl)-D(L)-amino acids by esterification of the COOH group with p-nitrophenol and dicyclohexylcarbodiimide. The calix[4]arenes and amino acid esters were confirmed by elemental analysis, specific rotation, IR and NMR spectroscopic measurements. With respect to the hydrolysis of Z-D(L)-Trp-PNP mediated by the calix[4]arenes in the presence of Z-L-Phe-OH, a little inhibition effect was observed on the basis of the rate constants. Particularly, the hydrolysis of D-substrate tended to be slightly slower than that of L-substrate. Furthermore, the computer modeling (molecular mechanics) studies indicated that the calix[4]arene would adopt a "cone" conformation. These results suggest that the calix[4]arenes could form inclusion complexes with Z-D(L)-Trp-PNP. Probably, the stereochemical arrangements of the chiral calix[4]arenes may induce the enantioselectivity for the hydrolysis of Z-D(L)-Trp-PNP.

通过对位取代苯酚二聚体的裂解缩合反应合成了具有三种不同上缘取代基的手性杯[4]芳烃（5-叔丁基-11-甲基-17,23-二苯基-25,26,27,28-四羟基杯[4]芳烃）的外消旋混合物 (2-(5-甲基水杨基)-4-叔丁基苯酚和3-(3-羟甲基-5-苯基水杨基)-5-苯基-2-羟基苯甲醇)根据K.No和同事的多步方法。另一方面，通过对硝基苯酚和二环己基碳二亚胺对N-(苄氧基羰基)-D(L)-氨基酸的COOH基团进行酯化，制备氨基酸酯(Z-D(L)-Ala-PNP、Z-D(L)-Trp-PNP)。通过元素分析、比旋光度、红外和核磁共振光谱测量证实了杯[4]芳烃和氨基酸酯。对于在Z-L-Phe-OH存在下由杯[4]芳烃介导的Z-D(L)-Trp-PNP的水解，根据速率常数观察到一点抑制作用。特别是，D-底物的水解往往比L-底物的水解稍慢。此外，计算机建模（分子力学）研究表明杯[4]芳烃将采用“锥体”构象。这些结果表明杯[4]芳烃可以与Z-D(L)-Trp-PNP形成包合物。手性杯[4]芳烃的立体化学排列可能会诱导 Z-D(L)-Trp-PNP 水解的对映选择性。