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

•We quantified the electrophilic reactivity for four aromatic triflones.•We examined the substitutents effect on the electrophilic strength.•Ranking the neutral electro-deficient electrophiles in Mayr's scale.•Increasing the scope and the applications of the Mayr equation.•Expanding the range of coupling reactions.

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.

Graphical abstractApplying the general approach to nucleophilicity/electrophilicity developed by Mayr et al., the E parameters, quantifying the electrophilic reactivity of four aromatic triflones, have been determined in acetonitrile, through kinetic investigations of σ-complexation and SNAr substitution reactions involving anilines and enamines as N- and C-nucleophiles.Figure optionsDownload full-size imageDownload as PowerPoint slide