Nonheme iron catalyst mimics heme-dependent haloperoxidase for efficient bromination and oxidation.

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  • Additional Information
    • Source:
      Publisher: American Association for the Advancement of Science Country of Publication: United States NLM ID: 101653440 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 2375-2548 (Electronic) Linking ISSN: 23752548 NLM ISO Abbreviation: Sci Adv Subsets: MEDLINE
    • Publication Information:
      Original Publication: Washington, DC : American Association for the Advancement of Science, [2015]-
    • Subject Terms:
      Oxidation-Reduction* ; Halogenation* ; Heme*/chemistry ; Heme*/metabolism ; Iron*/chemistry ; Iron*/metabolism ; Peroxidases*/metabolism ; Peroxidases*/chemistry ; Hydrogen Peroxide*/chemistry ; Hydrogen Peroxide*/metabolism; Catalysis
    • Abstract:
      The [Fe]/H 2 O 2 oxidation system has found wide applications in chemistry and biology. Halogenation with this [Fe]/H 2 O 2 oxidation protocol and halide (X - ) in the biological system is well established with the identification of heme-iron-dependent haloperoxidases. However, mimicking such halogenation process is rarely explored for practical use in organic synthesis. Here, we report the development of a nonheme iron catalyst that mimics the heme-iron-dependent haloperoxidases to catalyze the generation of HOBr from H 2 O 2 /Br - with high efficiency. We discovered that a tridentate terpyridine (TPY) ligand designed for Fenton chemistry was optimal for FeBr 3 to form a stable nonheme iron catalyst [Fe(TPY)Br 3 ], which catalyzed arene bromination, Hunsdiecker-type decarboxylative bromination, bromolactonization, and oxidation of sulfides and thiols. Mechanistic studies revealed that Fenton chemistry ([Fe]/H 2 O 2 ) might operate to generate hydroxyl radical (HO • ), which oxidize bromide ion [Br - ] into reactive HOBr. This nonheme iron catalyst represents a biomimetic model for heme-iron-dependent haloperoxidases with potential applications in organic synthesis, drug discovery, and biology.
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    • Accession Number:
      42VZT0U6YR (Heme)
      E1UOL152H7 (Iron)
      EC 1.11.1.- (Peroxidases)
      BBX060AN9V (Hydrogen Peroxide)
    • Publication Date:
      Date Created: 20241204 Date Completed: 20241204 Latest Revision: 20241207
    • Publication Date:
      20241209
    • Accession Number:
      PMC11616719
    • Accession Number:
      10.1126/sciadv.adq0028
    • Accession Number:
      39630909