RT Journal Article
T1 Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp3)−H Bond Insertion
A1 Díaz Jiménez, Àlex
A1 Monreal Corona, Roger
A1 Poater, Albert
A1 Álvarez Martínez, María
A1 Borrego, Elena
A1 Pérez Romero, Pedro José
A1 Caballero Bevia, Ana
A1 Roglans, Anna
A1 Pla Quintana, Anna
AB 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.
PB Wiley
SN 1433-7851
SN 1521-3773 (electrónico)
YR 2022
FD 2022
LK https://hdl.handle.net/10272/21798
UL https://hdl.handle.net/10272/21798
LA eng
NO Díaz‐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.202215163
NO We are grateful for financial support from the Ministerio de Ciencia e Innovación (PGC2018-097722-B-I00, PID2020113797RB-C21 and PID2020-113711GB-I00 MCIN/AEI/ 10.13039/501100011033 and FPU grants to A.D.-J. and R.M.-C.) and the Generalitat de Catalunya (Project 2017SGR-39). We also thank Junta de Andalucía (P18-1536) and Universidad de Huelva (P.O.Feder UHU202024). A.P.Q. and A.P. are Serra Húnter Fellows and A.P. thanks ICREA Academia Prize 2019. M.A. thanks Junta de Andalucia for a postdoctoral fellowship. E.B. thanks Cátedra Cepsa-Universidad de Huelva for financial support.
DS Repositorio Institucional de la Universidad de Huelva
RD 1 jun 2026