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Mechanistic Studies on the Gold-Catalyzed Intramolecular Hydroalkylation of Ynamides to Indenes

par Annibaletto, Julien ;Jacob, Clément ;Thilmany, Pierre ;Loison, Anaïs ;Escorihuela, Jorge;Evano, Gwilherm
Référence ACS Omega, 9, page (51690-51700)
Publication Publié, 2024-12-17

Article révisé par les pairs

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Résumé :

An in-depth experimental and computational study to rationalize the mechanism underlying the gold-catalyzed intramolecular hy-droalkylation of ynamides to indenes is reported. Evaluating the reactivity of a set of deuterated ynamides and gold complexes al-lowed to get valuable insights on the mechanism of this reaction, while DFT calculations allowed to determine a plausible reaction pathway for this unprecedented transformation. This pathway involves the activation of the ynamide followed by a [1,5]-hydride shift from the highly reactive, in situ generated keteniminium ion and a subsequent cyclization before deprotonation followed by a final protodeauration. According to DFT calculations, the initial [1,5]-hydride shift was identified as the rate-determining step of the reac-tion mechanism. Additionally, computational studies allowed to rationalize the differences in reactivity of various ynamides and the pivotal role of gold complexes for the catalysis of this reaction.