以鈉離子導引兩條二乙二醇鏈正交排列並合成[2]交環烷

Synthesis of a [2]Catenane from the Sodium Ion Templated Orthogonal Arrangement of Two Diethylene Glycol

董順德(Shun-Te Tung)

指導教授 ： 邱勝賢

國立臺灣大學/理學院/化學研究所/博士(2017年)

https://doi.org/10.6342/NTU201704228

摘要

第一部分：以鈉離子導引兩條二乙二醇鏈正交排列並合成[2]交環烷
如欲有效率地建構[2]交環烷，常藉由模板導引法將分子個別的前驅物元件適當排列，然而並沒有任何以鹼金屬離子為模板的先例。在本文中，我們報導了以五個元件 (兩個二醛分子、兩個二胺分子、一個鈉離子) 自組裝合成[2]交環烷。這種簡單而有效的合成策略能將鈉離子作為模板，使含有二乙二醇鏈的二胺分子兩兩正交排列，並與二醛分子反應生成[2]交環烷。利用硼氫化鈉還原不穩定的亞胺鍵，以分離並鑑定穩定的[2]交環烷。

第二部分：環狀[2]交環烷二聚體之合成研究
先前我們報導了以鈉離子為模板，使含有二乙二醇鏈的二胺分子兩兩正交排列，並與二醛分子反應生成[2]交環烷。於此，我們希望能延伸此系統，設計具有特定角度的四醛分子，搭配二胺分子與鈉離子模板，以動態亞胺鍵一鍋化自組裝成環狀[2]交環烷寡聚體。利用硼氫化鈉還原不穩定的亞胺鍵，並甲基化所得的二級胺，以分離並鑑定由共價鍵建構且穩定的環狀[2]交環烷二聚體。

關鍵字

交環烷 ； 鈉離子模板 ； 自組裝

並列摘要

Part I : Synthesis of a [2]Catenane from the Sodium Ion Templated Orthogonal Arrangement of Two Diethylene Glycol.
An important feature for the efficient construction of a [2]catenane is the appropriate alignment of the individual precursor molecular components by template-directed synthesis. However, we were unaware of any examples of the use of alkali metal ions as a template. Herein, we report the synthesis of a [2]catenane from five components (two diamines, two dialdehydes, one Na+ ion). This simple and efficient synthesis strategy makes use of a Na+ ion as a template to align two di(ethylene glycol)-containing diamines in an orthogonal manner, which can then react with two units of dialdehyde to generate [2]catenanes. NaBH4 mediated reduction of the labile imino bonds enabled the isolation and characterization of the [2]catenane as a stable compound.

Part II : Synthesis of a Cyclic [2]Catenane Dimer.
Previously, we reported that Na+ ions can template the orthogonal alignment of two di(ethylene glycol)-containing diamines, which can then react with two units of dialdehyde to generate [2]catenanes. We wished to extend this concept by applying the tetraaldehyde with specific angle for the corresponding reaction with diamine and Na+ ions to dynamically synthesis cyclic [2]catenane oligomers. NaBH4 mediated reduction of the labile imino bonds of these cyclic [2]catenane oligomers, followed by methylation of the resulting secondary amino groups enabled the isolation and characterization of a dimeric cyclic [2]catenane as stable, covalently linked compounds.

並列關鍵字

catenane ； sodium Ion templated ； self-assembly

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