Department of Chemistry, University of California-Davis, 1 Shields Ave, Davis, California 95616, United States.
J Am Chem Soc. 2022 Aug 10;144(31):13996-14004. doi: 10.1021/jacs.2c04683. Epub 2022 Jul 27.
Differences in entropies of competing transition states can direct kinetic selectivity. Understanding and modeling such entropy differences at the molecular level is complicated by the fact that entropy is statistical in nature; i.e., it depends on multiple vibrational states of transition structures, the existence of multiple dynamically accessible pathways past these transition structures, and contributions from multiple transition structures differing in conformation/configuration. The difficulties associated with modeling each of these contributors are discussed here, along with possible solutions, all with an eye toward the development of portable qualitative models of use to experimentalists aiming to design reactions that make use of entropy to control kinetic selectivity.
竞争过渡态熵的差异可以指导动力学选择性。在分子水平上理解和模拟这种熵差异很复杂，因为熵本质上是统计性的；也就是说，它取决于过渡结构的多个振动状态，通过这些过渡结构的多个动态可访问途径的存在，以及构象/构型不同的多个过渡结构的贡献。本文讨论了建模这些贡献者中的每一个所涉及的困难，以及可能的解决方案，所有这些都是为了开发可用于实验人员的便携式定性模型，旨在设计利用熵来控制动力学选择性的反应。
