四环周环环加成反应的计算设计及具有多个分支的势能面的性质
Computational Design of a Tetrapericyclic Cycloaddition and the Nature of Potential Energy Surfaces with Multiple Bifurcations.
作者信息
Martin-Somer Ana, Xue Xiao-Song, Jamieson Cooper S, Zou Yike, Houk K N
机构信息
Departamento de Química Física Aplicada, Facultad de Ciencias, Módulo 13, Universidad Autónoma de Madrid, Campus de Excelencia UAM-CSIC Cantoblanco, 28049 Madrid, Spain.
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, United States.
出版信息
J Am Chem Soc. 2023 Feb 9;145(7):4221-30. doi: 10.1021/jacs.2c12871.
An ambimodal transition state (TS) that leads to formation of four different pericyclic reaction products ([4 + 6]-, [2 + 8]-, [8 + 2]-, and [6 + 4]-cycloadducts) without any intervening minima has been designed and explored with DFT computations and quasiclassical molecular dynamics. Direct dynamics simulations propagated from the ambimodal TS show the evolution of trajectories to give the four cycloadducts. The topography of the PES is a key factor in product selectivity. A good correlation is observed between geometrical resemblance of the products to the ambimodal TS (measured by the RMSD) and the ratio of products formed in the dynamics simulations.
一种双模态过渡态（TS）已被设计出来，并通过密度泛函理论（DFT）计算和准经典分子动力学进行了探索。这种过渡态能够导致四种不同的周环反应产物（[4 + 6]-、[2 + 8]-、[8 + 2]-和[6 + 4]-环加成物）的形成，且中间没有任何极小值。从双模态过渡态开始的直接动力学模拟显示了生成四种环加成物的轨迹演变。势能面（PES）的拓扑结构是产物选择性的关键因素。在动力学模拟中形成的产物比例与产物和双模态过渡态的几何相似性（通过均方根偏差RMSD衡量）之间观察到了良好的相关性。
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