Electrolytic C–H Oxygenation via Oxidatively Induced Reductive Elimination in Rh Catalysis

Herein, we describe the development of a Rh-catalyzed C–H acyloxylation under mild electrolytic conditions. Anodic oxidation of a key rhodacyclic carboxylate intermediate was found to enable the product-releasing C–O bond-forming reductive elimination process. An accumulation of carboxylate near the electrode surface was rationalized to further induce the desired C–O bond formation, allowing an ambient catalytic C–H oxygenation using stoichiometric amounts of readily accessible carboxylic acid coupling partners.