Dynamic multi-component covalent assembly for the reversible binding of secondary alcohols and chirality sensing.
Dynamic multi-component covalent assembly for the reversible binding of secondary alcohols and chirality sensing.
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DOI：
10.1038/nchem.1198
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发表时间：
2011-11-13
期刊：
影响因子：
21.8
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中科院分区：
文献类型：
--
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可逆共价键通常用于创建新的超分子结构，多组分组装和传感集成。尽管动态共价体系取得了显著的成功，但高强度单醇的可逆结合是具有挑战性的。在这里，我们表明羰基活化和半胺醚稳定的策略可以体现在一个四组分可逆组装中，该组装产生了一个四齿配体，并结合了具有极高亲和力的仲醇。有证据表明，导致醇结合和交换的中间体是一种铝离子。此外，为了证明这种组装过程的使用，我们探索了手性传感和对映体过量的测定。由手性单醇引起的配体扭曲会在表明醇的手性的圆二色光谱中产生较大的棉花效应。本研究揭示的策略应被证明广泛适用于将醇纳入超分子结构构建。
Reversible covalent bonding is often employed for the creation of novel supramolecular structures, multi-component assemblies, and sensing ensembles. In spite of remarkable success of dynamic covalent systems, the reversible binding of a mono-alcohol with high strength is challenging. Here we show that a strategy of carbonyl activation and hemiaminal ether stabilization can be embodied in a four-component reversible assembly that creates a tetradentate ligand and incorporates secondary alcohols with exceptionally high affinity. Evidence is presented that the intermediate leading to binding and exchange of alcohols is an iminium ion. Further, to demonstrate the use of this assembly process we explored chirality sensing and enantiomeric excess determinations. An induced twist in the ligand by a chiral mono-ol results in large Cotton effects in the circular dichroism spectra indicative of the alcohol’s handedness. The strategy revealed in this study should prove broadly applicable for the incorporation of alcohols into supramolecular architecture construction.
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