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

[img]
Preview
 Text (McLellan-etal-ACIE-2017-LiTMP-trans-metal-trapping-of-fluorinated-aromatic-molecules)
McLellan_etal_ACIE_2017_LiTMP_trans_metal_trapping_of_fluorinated_aromatic_molecules.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo
Download (848kB)| Preview

    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.

    Creators(s): 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
    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:21 Feb 2020 04:50
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/61152
    Export data:
    CORE (COnnecting REpositories)