The synthesis and characterization of original NHC ligands based on an imidazo[1,5‐a]pyridin‐3‐ylidene (IPy) scaffold functionalized with a flanking barbituric heterocycle is described as well as their use as tunable ligands for efficient gold‐catalyzed C−N, C−O, and C−C bond formations. High activity, regio‐, chemo‐, and stereoselectivities are obtained for hydroelementation and domino processes, underlining the excellent performance (TONs and TOFs) of these IPy‐based ligands in gold catalysis. The gold‐catalyzed domino reactions of 1,6‐enynes give rise to functionalized heterocycles in excellent isolated yields under mild conditions. The efficiency of the NHC gold 5Me complex is remarkable and mostly arises from a combination of steric protection and stabilization of the cationic AuI active species by ligand 1Me.

The synthesis and characterization of original NHC ligands based on an imidazo[1,5-a]pyridin-3-ylidene (IPy) scaffold functionalized with aflanking barbituric heterocycle is described as well as their use as tunable ligands for efficient gold-catalyzed CÀN, CÀO, and CÀCb ond formations.H igh activity,regio-, chemo-, and stereoselectivities are obtained for hydroelementation and domino processes,u nderlining the excellent performance (TONs and TOFs) of these IPy-based ligands in gold catalysis.The gold-catalyzed domino reactions of 1,6-enynes give rise to functionalizedh eterocycles in excellent isolated yields under mild conditions.T he efficiency of the NHC gold 5 Me complex is remarkable and mostly arises from acombination of steric protection and stabilization of the cationic Au I active species by ligand 1 Me . Scheme 2. Gold-catalyzed intermolecularaddition of amine and carboxylic acids to phenylacetylene and 1-dodecyne.Scheme 3. Au-catalyzed domino cyclization/nucleophilic addition of 1,6-enynesw ith various nucleophiles. [a] in CH 2 Cl 2 ;n .i. not isolated.

Coupling between 5‐bromoimidazo[1,5‐a]pyridinium salts and malonate or arylacetate esters leads to a facile and straightforward access to the new mesoionic, fused, tricyclic system of imidazo[2,1,5‐cd]indolizinium‐3‐olate. Mechanistic studies show that the reaction pathway consists of nucleophilic aromatic substitution on the cationic, bicyclic heterocycle by an enolate‐type moiety and in the nucleophilic attack of a transient free N‐heterocyclic carbene (NHC) species on the ester group; the relative order of these two steps depends on the nature of the starting ester. This work highlights the valuable implementation of free NHC species as key intermediates in synthetic chemistry, beyond their classical use as stabilizing ligands or organocatalysts.