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.