Evaluation of the Synthetic Scope and the Reaction Pathways of Proton‐Coupled Electron Transfer with Redox‐Active Guanidines in C−H Activation Processes
Ute Wild, Petra Walter, Olaf Hübner, Elisabeth Kaifer, Hans‐Jörg Himmel
Abstract
Proton-coupled electron transfer (PCET) is currently intensively studied because of its importance in synthetic chemistry and biology. In recent years it was shown that redox-active guanidines are capable PCET reagents for the selective oxidation of organic molecules. In this work, the scope of their PCET reactivity regarding reactions that involve C-H activation is explored and kinetic studies carried out to disclose the reaction mechanisms. Organic molecules with potential up to 1.2 V vs. ferrocenium/ferrocene are efficiently oxidized. Reactions are initiated by electron transfer, followed by slow proton transfer from an electron-transfer equilibrium.
Topics & Concepts
Proton-coupled electron transferElectron transferRedoxChemistryReagentReactivity (psychology)ProtonFerroceneMoleculePhotochemistryKineticsCombinatorial chemistryElectrochemistryOrganic chemistryPhysical chemistryElectrodeAlternative medicineMedicineQuantum mechanicsPhysicsPathologyMetal-Catalyzed Oxygenation MechanismsPorphyrin and Phthalocyanine ChemistryCO2 Reduction Techniques and Catalysts