C-N bond activation and ring opening of a saturated N heterocyclic carbene via lateral alkali-metal-mediated metallation (AMMM)

Hernán‐gómez, Alberto and Kennedy, Alan r. and Hevia, Eva (2017) C-N bond activation and ring opening of a saturated N heterocyclic carbene via lateral alkali-metal-mediated metallation (AMMM). Angewandte Chemie International Edition, 56 (23). pp. 6632-6635. ISSN 1521-3773 (https://doi.org/10.1002/anie.201702246)

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Abstract

Combining alkali-metal mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes = [:C{N(2,4,6-Me3C6H2)CH2}2]) with group 1 alkyl bases suggest this destructive process is triggered by lateral metallation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH2SiMe3)2 and Al(TMP)iBu2), key intermediates in this process have been isolated and structurally defined.

ORCID iDs

Hernán‐gómez, Alberto, Kennedy, Alan r. and Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506;
  • Item type:Article
    ID code:60497
    Dates:
    Date
    Event
    1 June 2017
    Published
    19 April 2017
    Accepted
    Notes:This is the peer reviewed version of the following article: Hernán-Gómez, A., Kennedy, A., & Hevia, E. (2017). C-N bond activation and ring opening of a saturated N heterocyclic carbene via lateral alkali-metal-mediated metallation (AMMM). Angewandte Chemie International Edition. 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:24 Apr 2017 08:42
    Last modified:11 Nov 2024 11:41
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/60497
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