Gold-Zinc Cooperative Catalysis for Seven-exo-dig Hydrocarboxylation of Internal Alkynes

Seven-exo-dig hydrocarboxylation of nonactivated internal alkynes with conformationally flexible linker chains was achieved with cooperative gold-zinc catalysts composed of an imidazo[1,5-a]pyridinylidene ligand including a bipyridine coordination site at the C5 position. A proximity effect of the gold and zinc sites was essential for their high catalytic activity, in which the internal alkyne activated by the cationic gold species was attacked by the carboxylic acid deprotonated by the basic zinc site. Using a gold(I)-complex with a bulky aromatic N-substituent, 2,6-dibenzhydryl-4-methylphenyl group, for the NHC ligand facilitated seven-membered ring formation while minimizing intermolecular hydrocarboxylation as an undesired side reaction. The reaction mechanism was investigated by quantum chemical calculations.