芳杯冠醚修飾聯二萘酚衍生物之合成與其對胺基醇之掌性辨識研究

Abstract

論文主要研究之方向為兩部份，分別為掌性芳杯之合成與對掌 性分子之辨識研究，以及掌性芳杯對金屬離子之感測討論。 首先，我們成功合成出在芳杯下緣鄰位具有 (S)-(-)-BINOL 冠醚 之芳杯衍生物(S)-(-)-42a-b，以及進一步衍生化至(S)-(-)-43a-b、 (S)-(-)-44a-b 與(S)-(-)-49a-b，分別進行一系列紫外可見光光譜之量測，將化合物(S)-(-)-44a-b 與 (S)-(-)-49a 針對八類掌性小分子50-57進行螢光光譜篩選，觀察到螢光增強的現象，利用非線性回歸方法得到主客間之結合常數。以(S)-(-)-44a 而言，由大至小分別為：(S)-53 (S)-55 (S)-54 (S)-52 (S)-50 (S)-51 (S)-56 □ (S)-57，從中討論並且比較其掌性辨識能力，發現其中對53 有最佳的辨識效果（Kass(R)= 3.41*104 M-1, Kass(S) = 3.21*105 M-1, Kass(R)/Kass(S) = 1/9.41）。另外，在與其他客體的錯合中，我們可以歸納整理出各種情況之辨識特性，希望藉由相互比較來推論得到合理的錯合模式並探究影響掌性辨識的行為因素。

In this thesis, a series of binaphthyl-derived chiral calix[4]crowns were synthesized and their recognition abilities toward chiral amino alcohols and metal ions were studied. We have synthesized a series of (S)-(-)-binaphthyl-appended calix[4]crown-n ether (n = 6, 8) 41-49, which were substituted with mono- or proximal bis-carboxyl groups. The complexation properties of binaphthyl hosts (S)-(-)-44a-b and (S)-(-)-49a toward chiral amines, amino alcohols, alcohols and diols 50-57 were investigated by the UV-visible, fluorescence and CD spectroscopies. Possible binding modes of these chiral hosts toward amino alcohols 50 and 52-55 were discussed. The association constants (Kass)63 of 44a, 44b or 49a with chiral guest molecules were calculated by the nonlinear fitting method of the fluorescence spectra. Furthermore, the binding ratio of 44a-b and 49a with chiral guests were determined by Job plots. The results showed that the binding abilities of 44a toward guests decrease in the order of (S)-53 (S)-55 □ (S)-54 □ (S)-52 □ (S)-50 (S)-51 (S)-56 □ (S)-57. Furthermore, 44a exhibited a great performance for 53 in enantiomeric discrimination (Kass(R) = 3.41*104 M-1, Kass(S) = 3.21*105 M-1, Kass(R)/Kass(S) = 1/9.41). The comparisons of these complexes would gives an insight into the chiral recognition.