Jump to main content
Jump to site search

Issue 10, 2016
Previous Article Next Article

The mechanism of Claisen rearrangement of allyl phenyl ether from the perspective of topological analysis of the ELF

Author affiliations

Abstract

The Claisen rearrangement of allyl phenyl ether to 6-(prop-2-en-1-yl) cyclohexa-2,4-dien-1-one has been studied by means of Bonding Evolution Theory (BET), which combines the topological analysis of the electron localization function (ELF) and catastrophe theory. The reaction can be presented as consisting of 10 main steps separated by fold and cusp catastrophes. The description of the mechanism of C–O bond breaking is complicated and depends on the DFT method used. It proceeds through a heterolytic cleavage (B3LYP, M052x) with the formation of the V3(O) non-bonding basin in step II (M052x) or with electron density resonating between oxygen and carbon atoms in step II (B3LYP). The C–C bond between the allyl group and the phenol ring is formed after the TS in step VIII. The reaction is terminated by the formation of two localized C[double bond, length as m-dash]C bonds in the phenyl ring in steps IX and X. The localization of Vi=1,2(C,C) basins – typical of localized double bonds – in the phenyl ring proves the process of dearomatisation. The electronic structure of the transition structure distinguishes the non-bonding electron density concentrated in the vicinity of the C2 atom, represented by the V(C2) basin, with a population of 0.28e. This basin is a “bridgehead” for the “construction” of the C–C bond between the phenyl ring and the allyl group.

Graphical abstract: The mechanism of Claisen rearrangement of allyl phenyl ether from the perspective of topological analysis of the ELF

Back to tab navigation

Publication details

The article was received on 04 júl. 2016, accepted on 31 ágú. 2016 and first published on 31 ágú. 2016


Article type: Paper
DOI: 10.1039/C6NJ02074G
Author version
available:
Download author version (PDF)
Citation: New J. Chem., 2016,40, 8717-8726
  • Open access: Creative Commons BY license
  •   Request permissions

    The mechanism of Claisen rearrangement of allyl phenyl ether from the perspective of topological analysis of the ELF

    S. Berski and P. Durlak, New J. Chem., 2016, 40, 8717
    DOI: 10.1039/C6NJ02074G

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements