The Interplay Between n→π* Interaction and Dynamic Covalent Bond: Quantification and Modulation by Solvent Effects,Journal of the American Chemical Society

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The Interplay Between n→π* Interaction and Dynamic Covalent Bond: Quantification and Modulation by Solvent Effects
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-05-10 , DOI: 10.1021/jacs.9b01006
Hao Zheng _{1,

2} , Hebo Ye _{1,

3} , Xiaoxia Yu _{1,

2} , Lei You _{1,

3}

Affiliation

Orbital donor-acceptor interactions play critical roles throughout chemistry, and hence, their regulation and functionalization are of great significance. Herein we demonstrate for the first time the investigation of n→π* interactions through the strategy of dynamic covalent chemistry (DCC), and we further showcase its use in the stabilization of imine. The n→π* interaction between donor X and acceptor aldehyde/imine within 2-X-2'-formylbiphenyl derivatives was found to significantly influence the thermodynamics of imine exchange. The orbital interaction was then quantified through imine exchange, the equilibrium of which was successfully correlated with the difference in natural bond orbital stabilization energy of n→π* interactions of aldehyde and its imine. Moreover, the examination of solvent effects provided insights into the distinct feature of the modulation of n→π* interaction with aprotic and protic solvents. The n→π* interaction involving imine was enhanced in protic solvents due to hydrogen bonding with the solvent. This finding further enabled the stabilization of imine in purely aqueous solution. The strategies and results reported should find application in many fields, including molecular recognition, biological labeling, and asymmetric catalysis.

中文翻译：

n→π* 相互作用和动态共价键之间的相互作用：溶剂效应的量化和调制

轨道供体-受体相互作用在整个化学过程中起着关键作用，因此，它们的调节和功能化具有重要意义。在此，我们首次展示了通过动态共价化学 (DCC) 策略对 n→π* 相互作用的研究，并进一步展示了其在亚胺稳定中的应用。发现 2-X-2'-甲酰基联苯衍生物中供体 X 和受体醛/亚胺之间的 n→π* 相互作用显着影响亚胺交换的热力学。然后通过亚胺交换量化轨道相互作用，其平衡成功地与醛及其亚胺的 n→π* 相互作用的自然键轨道稳定能的差异相关联。而且，溶剂效应的检查提供了对 n→π* 与非质子和质子溶剂相互作用的调制的独特特征的见解。由于与溶剂的氢键作用，涉及亚胺的 n→π* 相互作用在质子溶剂中得到增强。这一发现进一步使亚胺在纯水溶液中稳定化。报告的策略和结果应在许多领域中得到应用，包括分子识别、生物标记和不对称催化。

更新日期：2019-05-10

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