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基于级联配合物的高效钾离子模板合成及[2]轮烷的可控破坏

Efficient potassium-ion-templated synthesis and controlled destruction of [2]rotaxanes based on cascade complexes.

作者信息

Han Tao, Chen Chuan-Feng

机构信息

Beijing National Laboratory for Molecular Sciences, Center for Chemical Biology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

出版信息

J Org Chem. 2008 Oct 3;73(19):7735-42. doi: 10.1021/jo801522f. Epub 2008 Aug 30.

Abstract

The triptycene-based macrotricyclic host can form pseudorotaxane-like cascade complexes with anthraquinone and its tetra-azide terminally functionalized derivative in the presence of potassium ions, which subsequently resulted in the synthesis of three novel potassium-ion-templated [2]rotaxanes 10-12 in high yields by the "threading followed by stoppering" approach. Since the potassium ions act not only as templates during the stoppering reactions but also as nonslipping chocks to shrink the inner diameter of the wheel cavity, the deslipping behaviors of the [2]rotaxanes with different triazole stoppers by peeling off the potassium ions with 18-crown-6 were further investigated. The results show that rotaxanes 10 and 11 can be destroyed, but under the same conditions the dumbbell and ring components of rotaxane 12 remain interlocked.

摘要

基于三蝶烯的大环三环主体在钾离子存在下可与蒽醌及其末端功能化的四叠氮衍生物形成类准轮烷级联配合物,随后通过“先穿线后封端”的方法以高产率合成了三种新型钾离子模板化的[2]轮烷10 - 12。由于钾离子不仅在封端反应中充当模板,还作为防滑楔块来缩小轮腔的内径,因此进一步研究了用18 - 冠 - 6剥离钾离子时不同三唑封端的[2]轮烷的解滑行为。结果表明,轮烷10和11可以被破坏,但在相同条件下,轮烷12的哑铃型和环型组分仍保持互锁状态。

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