Article révisé par les pairs
Résumé : Donor-substituted diarylcarbenium ions Ar2CH+ react with ynamides to give 1-amido-substituted allyl cations (alpha,beta-unsaturated iminium ions). Kinetic studies show that these adducts, which correspond to the addition of a CH bond across the CC bond, are formed stepwise with initial formation of keteniminium ions and subsequent 1,3-hydride shifts. The linear correlations between the second-order rate constants (lgk2, 20 °C) with the electrophilicity parameters E of the diarylcarbenium ions allow us to include ynamides in our comprehensive nucleophilicity scale and thus predict potential electrophilic reaction partners.