Electrooxidative Rhodium‐Catalyzed C−H/C−H Activation: Electricity as Oxidant for Cross‐Dehydrogenative Alkenylation

Abstract Rhodium(III) catalysis has enabled a plethora of oxidative C−H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we herein describe the first electrochemical rhodium‐catalyzed C−H activation that avoids hazardous chemical oxidants. Environmentally benign twofold C−H/C−H functionalizations were accomplished with weakly coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant and generating H 2 as the sole byproduct.