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Hydrocarbation of C≡C Bonds: Quantification of the Nucleophilic Reactivity of Ynamides

par Laub, Hans A;Evano, Gwilherm ;Mayr, Herbert
Référence Angewandte Chemie, 53, page (4968-4971)
Publication Publié, 2014

Article révisé par les pairs

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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.