Characterization of a Silver Vinylcarbene Intermediate in Carbene–Alkyne Metathesis and Its Concerted C(sp 2 )–H Bond Insertion

Journal of the American Chemical Society 2026 Open access

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Authors: Àlex Díaz‐Jiménez, Roger Monreal‐Corona, Arijit Saha, Andrea Álvarez-Núñez, Anna Company, Teodor Parella, Pedro J. Pérez, Ana Caballero, Anna Roglans, Albert Poater, Anna Pla‐Quintana
DOI: 10.1021/jacs.5c19806
Cited by: 0
References: 44

Abstract

High Resolution Image Download MS PowerPoint Slide Herein we present compelling evidence of the intervention of electrophilic silver vinylcarbenes in the carbene-alkyne metathesis (CAM) reaction, leading to a pivotal C(sp 2 )-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(sp 2 )-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.

Fields of Study & Subjects

Cyclopropane Reaction Mechanisms Catalytic Alkyne Reactions Chemical Reactions and Mechanisms

Publication details

Journal / source
Journal of the American Chemical Society
Volume
148
Issue
3
Pages
3689–3696
Publication date
12 January 2026
Language
EN