聯二萘酚冠醚芳杯衍生物之合成與其對掌性胺基與胺基醇之掌性辨識

Abstract

本論文已合成出芳杯下緣鄰位1,2-取代聯二萘酚冠醚衍生物，並在3,4-位置修飾雙羧酸根基團，經五步反應可得到芳杯 (R)-(+)-32，總產率約為15 %，所有化合物結構經氫、碳十三核磁共振光譜和質譜鑑定。 隨後分別對掌性胺類分子 (R/S)-38 (R/S)-1-phenylpropan-1-amine和掌性胺基醇分子 (R/S)-39 (R/S)-2-amino-2-phenylethanol進行氫核磁共振光譜滴定，以1：1錯合公式非線性最小平方迴歸法求得結合常數分別為83.7 M-1 ((R)-38)、8.5 M-1 ((S)-38)、23.8 M-1 ((R)-39)、12.0 M-1 ((S)-39)，並用Job Plot計算出主體化合物與客體分子的錯合比例為1：2。 由Gussian View進行理論計算結果，推測化合物客體分子與主體分子錯合模式為，一個酸基與一個銨鹽分子產生氫鍵作用。最後由實驗結果提出可能的錯合機制。 由於氫核磁共振光譜滴定計算Ka值誤差過大，參考Narumi與Hattori團隊對於胺類客體分子掌性辨識之研究法，對於客體分子 (R/S)-38、(R/S)-44、(R/S)-45與(R/S)-46進行實驗，比較化合物23與化合物 (R)-(+)-32的□□H(S-R) 數值，我們看出化合物 (R)-(+)-32之 □□H(S-R) 數值較化合物23來的小，顯示化合物 (R)-(+)-32掌性區分能力較差。

Binaphthylcrown-6 derivative of calix[4]arene at the 1,2-position of the lower rim was synthesized, which followed by attaching two carboxylate groups at the remaining phenols gave compound (R)-(+)-32. The synthetic route needed 5 steps and overall yield was about 15%. Structures of all products were confirmed by 1H-, 13C NMR and FAB-mass. We then investigated the complexation process of the title compound (R)-(+)-32 with (R/S)-1-phenylpropan-1-amine (R/S)-38 and (R/S)-2-amino-2 -phenylethanol (R/S)-39 via 1H NMR titration. From these data, we applied the nonlinear least-squares regression to calculate the association constants, and they are 83.7 M-1 ((R)-38), 8.5 M-1 ((S)-38), 23.8 M-1 ((R)-39), and 12.0 M-1 ((S)-39), respectively. The complexation ratio was determined to be H:G = 1:2 by Job plot using 1H NMR. Furthermore, theoretical calculation using the Gussain View was carried out which provided possible binding modes for the host (R)-(+)-32 and guests. Due to the large error for Ka determined by 1H NMR titration, we conducted the chiral recognition experiment by Narumi—Hattori method for (R/S)-38、(R/S)-44、(R/S)-45 and (R/S)-46. Comparing (R)-(+)-32 with 23 in □□H(S-R), we found the □□H(S-R) of (R)-(+)-32 were smaller than the □□H(S-R) of 23. It showed (R)-(+)-32 had little chiral recognition ability toward chiral amines.