Iron-Catalyzed C–H Oxygenation Using Perchlorate Enabled by Secondary Sphere Hydrogen Bonds
Writhabrata Sarkar, Andrew LaDuca, Jessica R. Wilson, Nathaniel K. Szymczak
Abstract
Perchlorate (ClO 4 – ) is a groundwater pollutant that is challenging to remediate. We report a strategy to use Fe(II) tris(2-pyridylmethyl)amine (TPA) complexes featuring appended aniline hydrogen bonds (H-bonds) to promote ClO 4 – reduction. These complexes facilitate oxygen atom transfer from ClO 4 – to PPh 3 and C–H oxygenation reactions of organic substrates. Catalytic reactions using 15 mol % afforded excellent yields for oxygenation of anthracene and cyclic alkyl aromatics, and this methodology tolerates aryl halides as well as heterocycles containing either O, S, or N.
Topics & Concepts
ChemistryCatalysisPerchlorateAlkylArylAnthraceneAnilineHalideAmine gas treatingHydrogen bondFerrousMedicinal chemistryAminationHydroaminationPhotochemistryOrganic chemistryInorganic chemistryMoleculeIonMetal-Catalyzed Oxygenation MechanismsSynthesis and Catalytic ReactionsVanadium and Halogenation Chemistry