Organocatalytic sulfoxidation

Stuart C. Davidson, Gabriel dos Passos Gomes, Leah R. Kuhn, Igor V. Alabugin, Alan Kennedy, Nick C.O. Tomkinson

Research output: Contribution to journalArticlepeer-review

Abstract

Treatment of a sulfide with a catalytic amount of a 1,3 diketone in the presence of silica sulfuric acid as a co-catalyst and hydrogen peroxide (50% aq) as the stoichiometric oxidant leads to the corresponding sulfoxide product. The reaction is effective for diaryl, aryl-alkyl and dialkyl sulfides and is tolerant of oxidisable and acid sensitive functional groups. Investigations have shown that the tris-peroxide 2, formed on reaction of pentane-2,4-dione with hydrogen peroxide under acidic reaction conditions, can oxidise two equivalents of sulfide using the exocyclic peroxide groups whereas the endocyclic peroxide remains intact. Calculations provide a mechanism consistent with experimental observations and suggest the reaction proceeds via an initial acid catalysed ring opening of a protonated tris-peroxide prior to oxygen transfer to a sulfur nucleophile.
Original languageEnglish
Article number131784
JournalTetrahedron
Volume78
Early online date24 Nov 2020
DOIs
Publication statusPublished - 8 Jan 2021

Keywords

  • peroxides
  • sulfoxidation
  • DFT calculations

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