Computational exploration of α-lactone rearrangements and the cyclic halonium zwitterion from bromination of acrylate anion in water: implicit vs. explicit solvation

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Abstract

In memory of Jonathan Williams, a valued colleague of incisive intellect (and regarded by undergraduates as ‘the better-looking Prof. Williams’ in the Department). Bromomethyloxiranone has a much larger repertoire of molecular acrobatics than previously recognised: conformational isomerism, degenerate rearrangement that exchanges O atoms in the α-lactone ring, and epimerisation, all of which occur with lower barriers than dyotropic rearrangement to the more stable β-lactone. DFT calculations (B3LYP/6-31 + G∗) with implicit solvation (PCM) by water predict the cyclic bromonium zwitterion (formally derived from addition of Br + to acrylate anion) to be a transition structure but QM/MM simulations, combining the same DFT method with explicit solvation by many MM water molecules and using molecular dynamics to obtain free-energy profiles and surfaces, reconfirms the status of the cyclic bromonium as an intermediate.

Original languageEnglish
Article number131989
Number of pages7
JournalTetrahedron
Volume84
Early online date9 Feb 2021
DOIs
Publication statusPublished - 26 Mar 2021

Keywords

  • Free-energy profile
  • Implicit and explicit solvation
  • Rearrangement
  • α-Lactone

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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