A computational study of anionic alkoxide–allene and amide–allene cyclizations

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Cumine, Florimond and Young, Allan and Reissig, Hans-Ulrich and Tuttle, Tell and Murphy, John A. (2017) A computational study of anionic alkoxide–allene and amide–allene cyclizations. European Journal of Organic Chemistry, 2017 (46). pp. 6867-6871. ISSN 1434-193X (https://doi.org/10.1002/ejoc.201701381)

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Abstract

Computational studies have been performed on potassium alkoxide-allenes, as well as potassium and lithium amido-allenes to probe the mechanism of their cyclizations to dihydrofurans and to 2,5-dihydropyrroles. A long-standing proposal envisaged electron transfer from dimsyl anions (formed by deprotonation of the solvent DMSO) but this pathway shows an exceptionally high kinetic barrier, while direct 5-endo-trig cyclization of the alkoxides and amides is much more easily achievable. The energy profiles for 4-exo-trig cyclizations onto the allenes are also explored, and the preferred formation of the observed five-membered products is rationalized.

ORCID iDs

Cumine, Florimond ORCID logoORCID: https://orcid.org/0000-0003-0158-7387, Young, Allan ORCID logoORCID: https://orcid.org/0000-0002-1525-4703, Reissig, Hans-Ulrich, Tuttle, Tell and Murphy, John A.;
  • Item type:Article
    ID code:63611
    Dates:
    Date
    Event
    15 December 2017
    Published
    11 October 2017
    Published Online
    11 October 2017
    Accepted
    Notes:This is the pre-peer reviewed version of the following article: Cumine, F., Young, A., Reissig, H-U., Tuttle, T., & Murphy, J. A. (2017). A computational study of anionic alkoxide–allene and amide–allene cyclizations. European Journal of Organic Chemistry, 2017(46), 6867-6871., which has been published in final form at https://doi.org/10.1002/ejoc.201701381. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:05 Apr 2018 08:58
    Last modified:11 Nov 2024 11:54
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/63611
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