Díaz Jiménez, ÀlexMonreal Corona, RogerPoater, AlbertÁlvarez Martínez, MaríaBorrego, ElenaPérez Romero, Pedro JoséCaballero Bevia, AnaRoglans, AnnaPla Quintana, Anna2023-03-162023-03-162022Díaz‐Jiménez, À., Monreal‐Corona, R., Poater, A., Álvarez, M., Borrego, E., Pérez, P. J., Caballero, A., Roglans, A., & Pla‐Quintana, A. (2022). Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp 3 )−H Bond Insertion. In Angewandte Chemie International Edition (Vol. 62, Issue 5). Wiley. https://doi.org/10.1002/anie.2022151631433-78511521-3773 (electrónico)https://hdl.handle.net/10272/21798The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp3)−H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process. A Tpx-containing silver complex first promotes the generation of a donor-acceptor silver carbene which triggers CAM, generating a subsequent donor-donor vinyl silver carbene species, which then undergoes a selective vinylogous C(sp3)−H bond insertion, leading to the synthesis of a new family of benzoazepines. Density functional theory (DFT) calculations unveil the reaction mechanism, which allows proposing that the C−H bond insertion reaction takes place in a stepwise manner, with the hydrogen shift being the rate determining step.engAtribución-NoComercial-SinDerivadas 3.0 Españahttp://creativecommons.org/licenses/by-nc-nd/3.0/es/journal article10.1002/anie.202215163open access23 Química