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標題: | 拓樸手性[2]交環烷之絕對結構鑑定及其酸/鹼控制之旋光度方向翻轉行為 Absolute Configurations of Topologically Chiral [2]Catenanes and the Acid/Base-Flippable Directions of Their Optical Rotations |
作者: | Tzu-Yi Tai 戴滋頤 |
指導教授: | 邱勝賢(Sheng-Hsien Chiu) |
關鍵字: | 絕對結構,交環烷,旋光度,開關,拓樸手性, absolute configuration,catenane,optical rotation,switch,topologically chiral, |
出版年 : | 2020 |
學位: | 博士 |
摘要: | 近年來,關於手性[2]車輪烷與[2]交環烷的建構,因其可互相轉換之構形異構物具有應用於鏡像選擇之感測及不對稱催化等方面的潛力,而引起了越來越多關注。過去三十年中,雖有許多[2]交環烷之合成被報導出來,但在這些分子當中,卻僅有少數具有拓樸手性。在本研究中,我們成功地以鈉離子為模板,合成出一個拓樸手性[2]交環烷,並且透過高效液相層析及X射線單晶繞射分析,明確地鑑定出拓樸手性[2]交環烷的兩個鏡像異構物之絕對結構。此外,我們更進一步展示透過依序加入酸使[2]交環烷的胺基被酸化及加入鹼使[2]交環烷的銨基被去質子化,此手性[2]交環烷之旋光度方向可在左旋 (負) 及右旋 (正) 之間被反覆地調控。這也是第一個拓樸手性[2]交環烷能夠展現類似胺基酸之 Clough-Lutz-Jirgensons (CLJ) 行為的例子。 The construction of chiral [2]rotaxanes and [2]catenanes has drawn increasing attention for the possibility of their switchable coconformers leading to innovative applications in enantioselective sensing and asymmetric catalysis. The past three decades have witnessed many syntheses of organic [2]catenanes, but only a few of these molecules have possessed topological chirality. Herein, we used a Na+ ion templating approach to synthesize a topologically chiral [2]catenane and then determined the absolute configurations of its two enantiomers unambiguously based on HPLC resolution and X-ray crystal analysis. We also reveal that the optical rotations of the two [2]catenane enantiomers can be flipped reversibly from positive (or negative) to negative (or positive), and vice versa, over several cycles of the sequential addition of acid and base to protonate/deprotonate their amine/ammonium functionalities, the first example of the Clough-Lutz-Jirgensons (CLJ) behavior for a mechanically interlocked topologically chiral catenane. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/15921 |
DOI: | 10.6342/NTU202002191 |
全文授權: | 未授權 |
顯示於系所單位: | 化學系 |
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