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

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

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19 Citations (Scopus)
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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.
Original languageEnglish
Pages (from-to)9566-9570
Number of pages5
JournalAngewandte Chemie International Edition
Volume56
Issue number32
Early online date17 Jul 2017
DOIs
Publication statusPublished - 1 Aug 2017

Keywords

  • aluminium
  • carbanions
  • fluoroaromatic compounds
  • gallium
  • metallation
  • structure elucidation

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