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.