Are There Carbenes in N‐Heterocyclic Carbene Organocatalysis?

Abstract Azolium cations are widely employed in organocatalysis to catalyse highly valuable synthetic processes in the presence of a base. These reactions are called “N‐heterocyclic carbene catalysis”, based on the assumption that they are initiated by the formation of a free carbene through deprotonation, which can then react with the substrates and thereby affect their reactivity to obtain the desired products. However, we herein provide evidence that an electrophilic aromatic substitution mechanism is energetically more favourable, in which the azolium cation reacts directly with the substrate, avoiding the formation of the free carbene in solution.