Theoretical simulations of heavy-atom kinetic isotope effects in aliphatic claisen rearrangement

Yuqing Xu*, Meishan Wang, Kin-Yiu WONG, Desheng Liu, Wenkai Zhao, Dongqing Zou, Xiaoteng Li

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The aliphatic Claisen rearrangement of allyl vinyl ether has attracted great interest for its broad applications in chemical synthesis and biosynthesis. Although it is well agreed that this reaction proceeds via a concerted, "chair-like"transition state, certain inconsistencies of kinetic isotope effect (KIE) data between experimental measurements and theoretical simulations or between independent experiments indicate that the nature and mechanism of this important reaction need to be investigated in more detail. In order to verify two independent sets of experimental data, we present theoretical calculations on heavy-atom KIE values of alipahtic Claisen rearrangement, using our recently developed path-integral method with the second-order Kleinert's variational perturbation theory, which goes beyond the traditional method for computing KIE values by employing the Bigeleisen equation. Amazingly, the results demonstrate that both sets of experimental measurements are correct, while the inconsistency originates from the fact that the aliphatic Claisen rearrangement undergoes similar but different mechanisms in gas and solution phases. Different experimental conditions will alter the actual reactant state by tuning the population distribution of reactant conformers. According to the comparison between experimental and theoretical results, a more clear reaction mechanism of aliphatic Claisen rearrangement is revealed.

Original languageEnglish
Pages (from-to)10678-10686
Number of pages9
JournalJournal of Physical Chemistry A
Volume124
Issue number51
DOIs
Publication statusPublished - 24 Dec 2020

Scopus Subject Areas

  • Physical and Theoretical Chemistry

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