An efficient approach for the direct synthesis of alkylated 4-hydroxycoumarin derivatives via Cu-catalyzed cascade dehydrogenation/conjugate addition sequence staring from simple saturated ketones and 4-hydroxycoumarins has been developed. This protocol features...

Carboxylic acids are abundant, low cost and environmentally friendly, direct convert carboxylic acids into valued‐added compounds are in high demand. Herein, we report a Rh(I) catalyzed direct decarbonylative borylation of aryl and alkyl carboxylic acid using TFFH as activator. This protocol features excellent functional‐group tolerance and a broad substrate scope including natural product and drugs. A gram‐scale decarbonylative borylation reaction of Probenecid is also presented. In addition, the utility of this strategy is highlighted by a one‐pot decarbonylative borylation/ derivatization sequence.