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

Nizar Elguesmi, Guillaume Berionni, Basim H. Asghar

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish
Pages (from-to)41-47
Number of pages7
JournalJournal of Fluorine Chemistry
Volume160
DOIs
Publication statusPublished - Apr 2014
Externally publishedYes

Keywords

  • Aromatic triflones
  • Electrophilicity
  • Kinetics
  • SAr reactions
  • Trifluoromethanesulfonyl group

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