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- Title
LiTMP Trans-Metal-Trapping of Fluorinated Aromatic Molecules: A Comparative Study of Aluminum and Gallium Carbanion Traps.
- Authors
McLellan, Ross; Uzelac, Marina; Kennedy, Alan R.; Hevia, Eva; Mulvey, Robert E.
- 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.
- Subjects
AROMATIC fluorine compounds; ALUMINUM; GALLIUM; CHEMICAL reactions; KETONES
- Publication
Angewandte Chemie, 2017, Vol 129, Issue 32, p9694
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201706064