Oxidative breakdown of iodoalkanes to catalytically active iodine species: A case study in the α-tosyloxylation of ketones

Wusheng Guo, Oriol Vallcorba, Adelina Vallribera, Alexandr Shafir, Roser Pleixats, Jordi Rius

Research output: Contribution to journalArticleResearchpeer-review

11 Citations (Scopus)

Abstract

Catalysis of the oxidative processes by iodoarenes has become a promising direction in synthesis. The mechanism, involving the well-known isolable hypervalent iodine species, is generally limited to aromatic iodides, since the corresponding aliphatic species are normally highly unstable. Nevertheless, in this work catalytic amount of several primary, secondary or tertiary iodoalkanes were found to promotes the α-tosyloxylation of a range of ketones with RSO 3 H, including aliphatic sulfonates. The process, was found to proceed through the oxidative breakdown of the iodoalkane to an inorganic catalytic species (likely IO - or IO 2- ), thus falling within the previously described catalysis using molecular iodine or inorganic iodides. The catalyst eventually becomes deactivated through the precipitation of an iodine overoxidation product, the structure of which was solved ab initio from the powder diffraction data as a hitherto unreported phase of the iodic acid (HIO 3 ). Iodine gets active: A catalytic amount of an iodoalkane promotes the α-tosyloxylation of a range of ketones with RSO 3 H, including aliphatic sulfonates. The process proceeds through the oxidative breakdown of the iodoalkane into an inorganic catalytic species (likely IO - or IO 2- ). The catalyst eventually becomes deactivated through iodine overoxidation, as exemplified by the formation of a white solid, proven to be a new phase of HIO 3 . mCPBA=meta-chloroperbenzoic acid. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Original languageEnglish
Pages (from-to)468-472
JournalChemCatChem
Volume6
Issue number2
DOIs
Publication statusPublished - 1 Feb 2014

Keywords

  • hypervalent compounds
  • iodine
  • iodoalkanes
  • powder diffraction
  • tosyloxylation

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