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Neighboring Amide Participation in Thioether Oxidation: Relevance to Biological Oxidation
journal contribution
posted on 2009-09-30, 00:00 authored by Richard S. Glass, Gordon L. Hug, Christian Schöneich, George S. Wilson, Larisa Kuznetsova, Tang-man Lee, Malika Ammam, Edward Lorance, Thomas Nauser, Gary S. Nichol, Takuhei YamamotoTo investigate neighboring amide participation in thioether oxidation, which may be relevant to brain oxidative stress accompanying β-amyloid peptide aggregation, conformationally constrained methylthionorbornyl derivatives with amido moieties were synthesized and characterized, including an X-ray crystallographic study of one of them. Electrochemical oxidation of these compounds, studied by cyclic voltammetry, revealed that their oxidation peak potentials were less positive for those compounds in which neighboring group participation was geometrically possible. Pulse radiolysis studies provided evidence for bond formation between the amide moiety and sulfur on one-electron oxidation in cases where the moieties are juxtaposed. Furthermore, molecular constraints in spiro analogues revealed that S−O bonds are formed on one-electron oxidation. DFT calculations suggest that isomeric σ*SO radicals are formed in these systems.
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oxidation peak potentialsspiro analoguescompoundElectrochemical oxidationbond formationbrain oxidative stressPulse radiolysis studiesamide participationamido moietiesNeighboring Amide Participationamide moietyBiological OxidationTocyclic voltammetryDFT calculationsmethylthionorbornyl derivativesgroup participationthioether oxidationThioether Oxidation
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