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转变后状态的分支在类Pummerer反应中引发动力学迂回。

Post-transition state bifurcations induce dynamical detours in Pummerer-like reactions.

作者信息

Hare Stephanie R, Li Ang, Tantillo Dean J

机构信息

University of California, Davis , USA . Email:

Shanghai Institute of Organic Chemistry , China.

出版信息

Chem Sci. 2018 Oct 4;9(48):8937-8945. doi: 10.1039/c8sc02653j. eCollection 2018 Dec 28.

DOI:10.1039/c8sc02653j
PMID:30627409
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6296359/
Abstract

A post-transition state bifurcation (PTSB) involved in a Pummerer-type rearrangement is characterized using density functional theory (DFT) calculations on potential energy stationary points and direct dynamics simulations. A sensitivity of the ratio of products produced this PTSB to solvent dielectric constant is revealed and implications of such a dependence for selectivity control of organic reactions are discussed.

摘要

利用密度泛函理论（DFT）对势能驻点进行计算并结合直接动力学模拟，对普默勒尔型重排中涉及的后过渡态分叉（PTSB）进行了表征。揭示了由该PTSB产生的产物比例对溶剂介电常数的敏感性，并讨论了这种依赖性对有机反应选择性控制的影响。

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