Source of Selectivity in Oxidative Cross‐Coupling of Aryls by Solvent Effect of 1,1,1,3,3,3‐Hexafluoropropan‐2‐ol

Solvents such as 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP) with a high capacity for donating hydrogen bonds generate solvates that enter into selective cross‐coupling reactions of aryls upon oxidation. When electric current is employed for oxidation, reagent effects can be excluded and a decoupling of nucleophilicity from oxidation potential can be achieved. The addition of water or methanol to the electrolyte allows a shift of oxidation potentials in a specific range, creating suitable systems for selective anodic cross‐coupling reactions. The shift in the redox potentials depends on the substitution pattern of the substrate employed. The concept has been expanded from arene–phenol to phenol–phenol as well as phenol–aniline cross‐coupling. This driving force for selectivity in oxidative coupling might also explain previous findings using HFIP and hypervalent iodine reagents.