Kong Wang-Yeuk, Hu Yun, Guo Wentao, Potluri Abhay, Schomaker Jennifer M, Tantillo Dean J
Department of Chemistry, University of California-Davis, Davis, California 95616, United States.
Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706, United States.
J Am Chem Soc. 2025 Feb 12;147(6):5310-5319. doi: 10.1021/jacs.4c16760. Epub 2025 Jan 30.
A post-transition state surface intersection (PTSSI) between radical and zwitterionic states that causes a bifurcation in the reaction pathway was discovered through density functional theory calculations on potential energy surfaces and ab initio molecular dynamics simulations of cycloadditions between a bicyclobutane and a triazolinedione (BCB-TAD). It was predicted that changes to the solvent polarity would enable control over the dynamic selectivity in this system; indeed, experimental evidence supported this prediction. This work not only provides new insights into an unusual type of post-transition state bifurcation, but also demonstrates how the nonstatistical dynamic effects that control selectivity for such reactions can be manipulated rationally to increase the yields of synthetically useful reactions.
通过对势能面的密度泛函理论计算以及双环丁烷与三唑啉二酮（BCB-TAD）之间环加成反应的从头算分子动力学模拟，发现了自由基态和两性离子态之间的后过渡态表面交叉（PTSSI），它导致了反应路径的分支。据预测，改变溶剂极性能够控制该体系中的动态选择性；实际上，实验证据支持了这一预测。这项工作不仅为一种不寻常的后过渡态分支类型提供了新的见解，还展示了如何合理地操纵控制此类反应选择性的非统计动态效应，以提高合成有用反应的产率。
