Dynamic Effects on Migratory Aptitudes in Carbocation Reactions
Dynamic Effects on Migratory Aptitudes in Carbocation Reactions
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DOI：
10.1021/jacs.0c11850
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发表时间：
2021-01-05
影响因子：
15
通讯作者：
Tantillo, Dean J.
中科院分区：
文献类型：
--
作者：
Feng, Zhitao;Tantillo, Dean J.
碳正离子重排反应在合成化学和生物合成化学中具有重要意义。在追求一个规模的固有迁移能力，考虑到动态效应，上坡和下坡从头算分子动力学（AIMD）模拟被用来检查竞争迁移事件的模型系统，旨在消除空间和电子偏见。这些模拟的结果相结合的势能表面形貌和变分过渡态理论计算的详细调查，以揭示迁移倾向的非统计动态效应的重要性。
Carbocation rearrangement reactions are of great significance to synthetic and biosynthetic chemistry. In pursuit of a scale of inherent migratory aptitude that takes into account dynamic effects, both uphill and downhill ab initio molecular dynamics (AIMD) simulations were used to examine competing migration events in a model system designed to remove steric and electronic biases. The results of these simulations were combined with detailed investigations of potential energy surface topography and variational transition state theory calculations to reveal the importance of nonstatistical dynamic effects on migratory aptitude.