@article{10272/21798, year = {2022}, url = {https://hdl.handle.net/10272/21798}, 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.}, organization = {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.}, publisher = {Wiley}, title = {Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp3)−H Bond Insertion}, doi = {10.1002/anie.202215163}, author = {Díaz Jiménez, Àlex and Monreal Corona, Roger and Poater, Albert and Álvarez Martínez, María and Borrego, Elena and Pérez Romero, Pedro José and Caballero Bevia, Ana and Roglans, Anna and Pla Quintana, Anna}, }