Iron-Electrocatalyzed C-H Arylations: Mechanistic Insights into Oxidation-Induced Reductive Elimination for Ferraelectrocatalysis.

TLDR: The unprecedented merger of electrosynthesis with iron‐catalyzed C−H activation through oxidation‐induced reductive elimination was described, accomplished at mild reaction temperatures with ample scope by the action of sustainable iron catalysts, employing electricity as a benign oxidant.

Abstract: Despite major advances, organometallic C-H transformations are dominated by precious 5d and 4d transition metals, such as iridium, palladium and rhodium. In contrast, the unique potential of less toxic Earth-abundant 3d metals has been underexplored. While iron is the most naturally abundant transition metal, its use in oxidative, organometallic C-H activation has faced major limitations due to the need for superstoichiometric amounts of corrosive, cost-intensive DCIB as the sacrificial oxidant. To fully address these restrictions, we describe herein the unprecedented merger of electrosynthesis with iron-catalyzed C-H activation through oxidation-induced reductive elimination. Thus, ferra- and manganaelectro-catalyzed C-H arylations were accomplished at mild reaction temperatures with ample scope by the action of sustainable iron catalysts, employing electricity as a benign oxidant.