RT Journal Article
T1 Characterization of a Silver Vinylcarbene Intermediate in Carbene−Alkyne Metathesis and Its Concerted C(sp2)−H Bond Insertion
A1 Díaz Jiménez, Àlex
A1 Pérez Romero, Pedro José
A1 Caballero Bevia, Ana
A1 Pla Quintana, Anna
AB Herein we present compelling evidence of the intervention of electrophilic silver vinylcarbenes in the carbene-alkyne metathesis (CAM) reaction, leading to a pivotal C(sp2)-H insertion process. The delicate equilibrium between the stability and reactivity of transient species is crucial for efficient detection. Through meticulous mechanistic exploration, we unveil that the mechanism for the C(sp2)-H insertion hinges on the substitution pattern. Indeed, it departs from the previously documented stepwise mechanism (involving Wheland intermediates), and it follows a concerted route, quite uncommon for this transformation.
PB American Chemical Society
SN 0002-7863
SN 1520-5126 (electrónico)
YR 2025
FD 2025
LK https://hdl.handle.net/10272/28056
UL https://hdl.handle.net/10272/28056
LA eng
NO Díaz-Jiménez, À., Monreal-Corona, R., Saha, A., Álvarez-Núñez, A., Company, A., Parella, T., Pérez, P. J., Caballero, A., Roglans, A., Poater, A., & Pla-Quintana, A. (2026). Characterization of a Silver Vinylcarbene Intermediate in Carbene–Alkyne Metathesis and Its Concerted C(sp2)–H Bond Insertion. Journal of the American Chemical Society, 148(3), 3689–3696. https://doi.org/10.1021/jacs.5c19806
NO The authors are grateful for finantial support from ProjectsPID2021-127423NB-I00 to A.P., PID2020-113711GB-I00 and PID2023-146849NB-I00 to A.P.-Q., PID2019-106699GB-I00 to A.Co., PID2020-113797RB-C21 and PID2023-146946NB-I00 to P.J.P. and A.C. funded by the Ministerio de Ciencia, Innovación y Universidades of Spain MCIU/AEI/10.13039/501100011033 and FEDER, UE,; RED2022-134074-T and RED2022-134331-T for network support, and from the Generalitat de Catalunya (2021-SGR-623 to A.R., 2021SGR-475 to A.Co. projects). We thank the Spanish Ministerio de Universidades for the predoctoral fellowship FPU18/02912 to À.D.-J. and FPU20/00707 to R.M.-C. and the Catalan Government for the predoctoral fellowship 2022 FI_B 00605 to A.A.-N. and a Beatriu de Pinós-AGAUR Postdoctoral grant (2022BP00051) to A.S.. A.P.-Q., A. Co, and A.P. are Serra Húnter Fellows and A.P. and A.Co. thank ICREA Academia Prizes.
DS Repositorio Institucional de la Universidad de Huelva
RD 14 jul 2026