Palladium-catalyzed C-H activation/C-O bond-forming reactions have emerged as attractive tools for organic synthesis. Typically, these reactions require strong chemical oxidants, which convert organopalladium(II) intermediates into the Pd or Pd oxidation state to promote otherwise challenging C-O reductive elimination. However, previously reported oxidants possess significant disadvantages, including poor atom economy, high cost, and the formation of undesired byproducts. To overcome these issues, we report an electrochemical strategy that takes advantage of anodic oxidation of Pd to induce selective C-O reductive elimination with a variety of oxyanion coupling partners.

Palladium-catalyzed arene C(sp)-H acetoxylation has emerged as a powerful tool to construct a carbon-oxygen (C-O) bond. However, the requirement of stoichiometric chemical oxidants for this transformation possesses a significant disadvantage. To solve this fundamental problem, we now report an anodic oxidation strategy to achieve arene C(sp)-H acetoxylation.