Exploiting Chloroform-COware Chemistry for Pd-Catalyzed Carbonylation of Naturally Occurring and Medicinally Relevant Phenols.

In this study, a ligand-free palladium-catalyzed carbonylation of phenols is conducted under ambient conditions, utilizing the "Chloroform-COware" chemistry. The developed methodology enables the conversion of diverse medicinally relevant phenols, encompassing both natural and synthetic derivatives, into their respective aryl ester counterparts. This transformation is achieved through the reaction with a broad spectrum of aryl and heteroaryl iodides. The protocol is characterized by its simplicity, generality, and wide substrate scope, delivering bioactive aryl ester derivatives in good to excellent yields. A direct comparison with the one-pot approach, resulting in poor yields of aryl esters, highlights the superior efficiency of the two-chamber setup (COware). Moreover, we successfully applied this two-chamber technique for gram-scale synthesis and postmodification of the synthesized ester to a pharmaceutically important benzocoumarin core.