LiTMP trans-metal-trapping of fluorinated aromatic molecules : a comparative study of Al and Ga carbanion traps

McLellan, Ross and Uzelac, Marina and Kennedy, Alan R. and Hevia, Eva and Mulvey, Robert E. (2017) LiTMP trans-metal-trapping of fluorinated aromatic molecules : a comparative study of Al and Ga carbanion traps. Angewandte Chemie International Edition, 56 (32). pp. 9566-9570. ISSN 1433-7851

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    Abstract

    Fluoro aromatic scaffolds pose a challenge to lithiation due to low stability of lithiated intermediates. Here we apply trans-metal-trapping (TMT) to a series of key fluorinated aromatics. In TMT, LiTMP performs the metallation, while an organometallic trap intercepts the emergent carbanion. This study contrasts the trapping abilities of iBu2AlTMP and Ga(CH2SiMe3)3, structurally mapping their TMT reactions and probing relative stabilities of metallated fluoroaromatic intermediates by NMR studies. Results show the installed Al-C(aryl) bonds are more prone to decomposition by benzyne formation and Li-F liberation, than the Ga-C(aryl) species. The latter are thus better for onward reactivity as demonstrated in cross-coupling reactions with benzoyl chloride that produce ketones.

    ORCID iDs

    McLellan, Ross ORCID logoORCID: https://orcid.org/0000-0001-9700-0258, Uzelac, Marina ORCID logoORCID: https://orcid.org/0000-0002-5060-7017, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506 and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
    • Item type:Article
      ID code:61152
      Dates:
      Date
      Event
      1 August 2017
      Published
      17 July 2017
      Published Online
      28 June 2017
      Accepted
      Keywords:aluminium, carbanions, fluoroaromatic compounds, gallium, metallation, structure elucidation, Chemistry, Chemistry(all)
      Subjects:Science > Chemistry
      Department:Faculty of Science > Pure and Applied Chemistry
      Depositing user: Pure Administrator
      Date deposited:29 Jun 2017 09:01
      Last modified:02 Nov 2021 01:48
      Related URLs:
      URI:https://strathprints.strath.ac.uk/id/eprint/61152
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