Characterization of a Silver Vinylcarbene Intermediate in Carbene−Alkyne Metathesis and Its Concerted C(sp2)−H Bond Insertion

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 efficien...

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Detalhes bibliográficos
Autores: Díaz Jiménez, Àlex, Pérez Romero, Pedro José, Caballero Bevia, Ana, Pla Quintana, Anna
Tipo de documento: artigo
Data de publicação:2025
País:España
Recursos:Universidad de Huelva (UHU)
Repositório:Arias Montano. Repositorio Institucional de la Universidad de Huelva
Idioma:inglês
OAI Identifier:oai:ariasmontano.uhu.es:10272/28056
Acesso em linha:https://hdl.handle.net/10272/28056
Access Level:Acceso aberto
Palavra-chave:Carbene compounds
Carbon
Hydrocarbons
Silver
Substituents
2306 Química Orgánica
2306.15 Mecanismos de Reacción
Descrição
Resumo: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.