LiTMP Trans-Metal-Trapping of Fluorinated Aromatic Molecules: A Comparative Study of Aluminum and Gallium Carbanion Traps

Ross McLellan, Marina Uzelac, Alan R. Kennedy, Eva Hevia, Robert E. Mulvey

Research output: Contribution to journalArticlepeer-review

41 Citations (SciVal)

Abstract

Fluoroaromatic 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 metalation, 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 metalated 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.

Original languageEnglish
Pages (from-to)9566-9570
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number32
DOIs
Publication statusPublished - 29 Jun 2017

Bibliographical note

Funding Information:
We thank the European Research Council (ERCStG, MixMetApps) and the EPSRC (EP/N011384/1) for their generous sponsorship of this research. Data supporting this research are openly available from https://doi.org/10.15129/ccd3e405-545a-494a-84ff-0a85986070a3.

Keywords

  • aluminum
  • carbanions
  • fluoroaromatic compounds
  • gallium
  • metalation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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