Department of Chemistry, University of Rochester, Rochester, New York14627, United States.
J Org Chem. 2023 Jan 6;88(1):106-115. doi: 10.1021/acs.joc.2c01893. Epub 2022 Dec 12.
Recent theoretical work and experiments at molecular junctions have provided a strong conceptualization for the effects of oriented electric fields (OEFs) on organic reactions. Depending on the axis of application, OEFs can increase (or decrease) the reaction rate or distinguish between isomeric pathways. Despite the conceptual elegance of OEFs, which may be applied externally or induced locally, as tools for catalyzing organic reactions, implementation in synthetically relevant systems has been hampered by inefficiencies in evaluating reaction sensitivity to field effects. Herein, we describe the development of the Automated Variable Electric-Field DFT Application (A.V.E.D.A.) for streamlined evaluation of a reaction's susceptibility to OEFs. This open-source software was designed to be accessible for nonexpert users of computational and programming tools. Following initiation by a single command (and with no subsequent intervention) the Linux workflow manages a series of density functional theory calculations and mathematical manipulations to optimize local-minimum and transition-state structures in oriented electric fields of increasing magnitude. The resulting molecular and reaction dipole moments, field-perturbed geometries, and net effective activation energies are compiled for user interpretation. Ten representative pericyclic reactions that showcase the development and evaluation of A.V.E.D.A. are described.
近期在分子结领域的理论研究和实验为定向电场（OEF）对有机反应的影响提供了强有力的概念化理解。根据应用的轴，OEF 可以增加（或减少）反应速率，或者区分异构途径。尽管 OEF 作为催化有机反应的工具具有概念上的优势，既可以外部施加，也可以局部诱导，但在合成相关体系中的应用受到评估反应对场效应敏感性的效率低下的阻碍。在此，我们描述了自动化可变电场密度泛函理论应用程序（A.V.E.D.A.）的开发，以简化对反应对 OEF 敏感性的评估。该开源软件旨在为计算和编程工具的非专家用户提供可访问性。在单个命令启动后（无需后续干预），Linux 工作流程管理一系列密度泛函理论计算和数学操作，以优化定向电场中增加幅度的局部最小值和过渡态结构。然后为用户解释编译得到的分子和反应偶极矩、受场干扰的几何形状以及有效净激活能。描述了十个代表性的周环反应，展示了 A.V.E.D.A. 的开发和评估。
