Neighboring amide participation in thioether oxidation: Relevance to biological oxidation

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 Yamamoto

Research output: Contribution to journalArticle

36 Scopus citations

Abstract

To 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.

Original languageEnglish (US)
Pages (from-to)13791-13805
Number of pages15
JournalJournal of the American Chemical Society
Volume131
Issue number38
DOIs
StatePublished - Oct 13 2009

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Glass, R. S., Hug, G. L., Schöneich, C., Wilson, G. S., Kuznetsova, L., Lee, T. M., Ammam, M., Lorance, E., Nauser, T., Nichol, G. S., & Yamamoto, T. (2009). Neighboring amide participation in thioether oxidation: Relevance to biological oxidation. Journal of the American Chemical Society, 131(38), 13791-13805. https://doi.org/10.1021/ja904895u