Bogazici University, Department of Chemistry, Bebek, 34342 Istanbul, Turkey.
Org Biomol Chem. 2018 Jan 31;16(5):796-806. doi: 10.1039/c7ob02253k.
Transient bicyclic aziridinium ions are known to undergo ring-expansion reactions, paving the way to functionalized nitrogen-containing heterocycles. In this study, the regioselectivity observed in the ring-expansion reactions of 1-azoniabicyclo[n.1.0]alkanes was investigated from a computational viewpoint to study the ring-expansion pathways of two bicyclic systems with different ring sizes. Moreover, several nucleophiles leading to different experimental results were investigated. The effect of solvation was taken into account using both explicit and implicit solvent models. This theoretical rationalization provides valuable insight into the observed regioselectivity and may be used as a predictive tool in future studies.
瞬态双环氮丙啶离子已知会发生环扩张反应，为含氮杂环的功能化铺平道路。在这项研究中，从计算的角度研究了 1-氮杂双环[n.1.0]烷的环扩张反应中观察到的区域选择性，以研究具有不同环大小的两个双环体系的环扩张途径。此外，还研究了导致不同实验结果的几种亲核试剂。使用显式和隐式溶剂模型考虑了溶剂化的影响。这种理论上的合理化提供了对观察到的区域选择性的有价值的见解，并可作为未来研究中的预测工具。
