Revealing the Mechanistic Features of an Electrosynthetic Catalytic Reaction and the Role of Redox Mediators through DFT Calculations and Microkinetic Modeling.

Organic electrosynthesis is an emerging field that provides original selectivity while adding features of atom economy, sustainability, and selectivity. Electrosynthesis is often enhanced by redox mediators or electroauxiliaries. The mechanistic understanding of organic electrosynthesis is however often limited by the low lifetime of intermediates and its difficult detection.

Charge-controlled Pd catalysis enables the -C-H activation and olefination of arenes.

The regioselective C-H activation of arenes remains one of the most promising techniques for accessing highly important functionalized motifs. Such functionalizations can generally be achieved through directed and non-directed processes. The directed approach requires a covalently attached directing group (DG) on the substrate to induce reactivity and selectivity and therefore intrinsically leaves a functional group at the point of attachment within the molecule, even after the tailored DG has been removed.