Pedrón Manuel, Sendra Jana, Ginés Irene, Tejero Tomás, Vicario Jose L, Merino Pedro
Instituto de Biocomputación y Física de Sistemas Complejos (BIFI), Universidad de Zaragoza, 50009 Zaragoza, Spain.
Departamento de Química Orgánica e Inorgánica, Universidad del País Vasco (UPV/EHU) P.O. Box 644, 48080 Bilbao, Spain.
Beilstein J Org Chem. 2023 Apr 20;19:477-486. doi: 10.3762/bjoc.19.37. eCollection 2023.
The contribution to the energy barrier of a series of tethers in transannular cycloadditions of cycloalkenes with hydrazones has been computationally studied by using DFT. The Houk's distortion model has been employed to evaluate the influence of the tether in the cycloaddition reaction. That model has been extended to determine the contribution of each tether and, more importantly, the effect exerted between them. In addition to the distortion induced by the tethers, the entropy effects caused by them has also been studied. The analysis of the evolution of the electron localization function along the reaction revealed the highly concerted character of the reaction.
通过使用密度泛函理论（DFT）对环烯烃与腙的跨环环加成反应中一系列连接基团对能垒的贡献进行了计算研究。采用霍克（Houk）的畸变模型来评估连接基团在环加成反应中的影响。该模型已被扩展以确定每个连接基团的贡献，更重要的是，确定它们之间的相互作用。除了连接基团引起的畸变外，还研究了它们引起的熵效应。沿着反应对电子定域函数演变的分析揭示了该反应具有高度协同的特征。
