Nitrogen‐Oxidized Tröger's Base Macrocyclic Arenes: Unprecedented Enantioselective Recognition in Water

作者：Xiaotong Liang, Ting Zhao, Yanling Shen, Li‐Zhi Fang, Long Chen, Da‐Yang Zhou, Wanhua Wu, Wanhua Wu, Cheng Yang · 发表于：Angewandte Chemie International Edition · 年份：2024 · DOI：10.1002/anie.202416975 · 被引用次数：19 · 研究领域：Molecular spectroscopy and chirality、Axial and Atropisomeric Chirality Synthesis、Spectroscopy and Quantum Chemical Studies

Achieving high enantioselectivity with synthetic receptors, particularly in water, remains a significant challenge despite the success seen in natural biological systems. In this study, we introduce a facile synthesis of Tröger's base (TB)-containing macrocyclic arenes (TBn), where TB units are linked via methylene bridges, providing the macrocycles with a rigid framework. Oxidation of enantiopure TBn yields corresponding chiral nitrogen oxides (TBnNO) with excellent water solubility, attributed to the high polarity of the N-O bond, surpassing the pH limitations of traditional ion-functionalized approaches. Remarkably, TBnNO exhibits exceptional enantioselective recognition toward a wide range of chiral guests in aqueous solution, achieving enantioselectivities as high as 41.0. The underlying mechanism involves a combination of hydrophobic interactions and steric effects caused by rigid chiral cavities. These findings highlight the potential of nitrogen-oxidized macrocycles as a transformative tool for supramolecular application in water.