Potent Reductants via Electron-Primed Photoredox Catalysis: Unlocking Aryl Chlorides for Radical Coupling
Nicholas G. W. Cowper, Colleen P. Chernowsky, Oliver P. Williams, Zachary K. Wickens
Abstract
We describe a new catalytic strategy to transcend the energetic limitations of visible light by electrochemically priming a photocatalyst prior to excitation. This new catalytic system is able to productively engage aryl chlorides with reduction potentials hundreds of millivolts beyond the potential of Na 0 in productive radical coupling reactions. The aryl radicals produced via this strategy can be leveraged for both carbon–carbon and carbon–heteroatom bond-forming reactions. Through direct comparison, we illustrate the reactivity and selectivity advantages of this approach relative to electrolysis and photoredox catalysis.
Topics & Concepts
ChemistryArylCatalysisPhotoredox catalysisPhotochemistryRadicalReactivity (psychology)ElectrolysisHeteroatomSynergistic catalysisSelectivityCombinatorial chemistryAryl radicalPhotocatalysisCarbon fibersOrganic chemistryComposite numberElectrodeAlternative medicinePhysical chemistryComposite materialAlkylPathologyRing (chemistry)MedicineElectrolyteMaterials scienceRadical Photochemical ReactionsSulfur-Based Synthesis TechniquesCatalytic C–H Functionalization Methods