Gas‐Free Amino‐ and Alkoxycarbonylation of Aryl Iodides in a Bioinspired Deep Eutectic Solvent with Mo(CO)6 as a Safe CO Source

The Pd‐catalyzed amino‐ and alkoxycarbonylation of aryl iodides has been exploited, for the first time, in a bioinspired Deep Eutectic Solvent and under gas‐free conditions, by using Mo(CO)6 as the CO source. The method allows for the preparation of carboxylic amides and esters in high yields (up to 99 %), short reaction time (2 h) and under mild reaction conditions (80 °C), with a low catalyst loading (2.5 mol %). Noteworthy, in the case of N‐hexylbenzamide, it has been demonstrated that both the catalyst and DES can be used for four consecutive runs, with a moderate decrease of catalytic efficiency. The methodology has been also applied to the preparation of an Active Pharmaceutical Ingredient used for the treatment of human scabies and lice. The synergy between a nature‐inspired ionic solvent and Mo(CO)6, as a solid source of carbon monoxide, allowed to develop a Pd‐catalyzed amino‐ and alkoxycarbonylation under mild reaction conditions and with an improved degree of sustainability.