Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp3)−H Bond Insertion |
| |
| Authors: | Àlex Díaz-Jiménez Roger Monreal-Corona Dr Albert Poater Dr María Álvarez Elena Borrego Prof Dr Pedro J Pérez Dr Ana Caballero Prof Dr Anna Roglans Dr Anna Pla-Quintana |
| |
| Institution: | 1. Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona (UdG), Facultat de Ciències, C/ Maria Aurèlia Capmany, 69, 17003 Catalunya Girona, Spain;2. Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, Edificio Robert H. Grubbs, Campus de El Carmen, 21007 Huelva, Spain |
| |
| Abstract: | The 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. |
| |
| Keywords: | 1-Benzoazepine C−H Bond Insertion Carbene-Alkyne Metathesis Silver Catalysis Vinylogous Reactivity |
|
|
