Mechanistic studies and quantification of the electrophilicity of aromatic triflones in σ-complexation and SNAr reactions

Nizar Elguesmi, Guillaume Berionni, Basim H. Asghar

Résultats de recherche: Contribution à un journal/une revueArticleRevue par des pairs

Résumé

The reactions of anilines (N-nucleophiles) and enamines (C-nucleophiles) with NO2 and SO2CF3 substituted aromatic triflones were investigated spectrophotometrically in acetonitrile at 20 C. We found that the second-order rate constants k1 related to the C-N and C-C bond forming step of these nucleophilic aromatic substitution reactions (SNAr) and σ-complexation reactions follow the three-parameter equation log k(20 C) = sN(N + E), allowing the determination of the electrophilicity E of such aromatic triflones for the first time. The ranking of these neutral electron-deficient compounds on the comprehensive electrophilicity scale defined by Mayr et al. reveals that the most electrophilic triflone, the 1,3,5-tris(trifluoromethanesulfonyl)benzene (TTSB), has an electrophilicity higher than that of the 1,3,5-trinitrobenzene (TNB) the common reference aromatic electrophile in anionic σ-complexation chemistry, by roughly 6 units of E. This finding holds promise for expanding the range of coupling reactions which can be envisioned between this series of electron-deficient neutral aromatics and nucleophiles.

langue originaleAnglais
Pages (de - à)41-47
Nombre de pages7
journalJournal of Fluorine Chemistry
Volume160
Les DOIs
Etat de la publicationPublié - avr. 2014
Modification externeOui

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