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 language | English |
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Pages (from-to) | 9566-9570 |
Number of pages | 5 |
Journal | Angewandte Chemie - International Edition |
Volume | 56 |
Issue number | 32 |
DOIs | |
Publication status | Published - 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.
Funding
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
- General Chemistry