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 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. ISSN 1433-7851 (In Press)

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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 ORCID logoORCID: https://orcid.org/0000-0001-8150-7249, Kennedy, Alan ORCID logoORCID: https://orcid.org/0000-0003-3652-6015 and Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506;
  • Item type:Article
    ID code:60497
    Dates:
    Date
    Event
    19 April 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
    Keywords:alkali-metal, C-N activation, metalation, mixed-metal chemistry, N-heterocyclic carbenes , SIMes, Chemistry, Chemistry(all)
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:24 Apr 2017 08:42
    Last modified:12 Sep 2023 03:21
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/60497
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