Peroxygenase-Catalyzed Oxyfunctionalization Reactions Promoted by the Complete Oxidation of Methanol

Yan Ni, Elena Fernández-Fueyo, Alvaro Gomez Baraibar, René Ullrich, Martin Hofrichter, Hideshi Yanase, Miguel Alcalde, W.J.H. van Berkel, Frank Hollmann*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

65 Citations (Scopus)


Peroxygenases catalyze a broad range of (stereo)selective oxyfunctionalization reactions. However, to access their full catalytic potential, peroxygenases need a balanced provision of hydrogen peroxide to achieve high catalytic activity while minimizing oxidative inactivation. Herein, we report an enzymatic cascade process that employs methanol as a sacrificial electron donor for the reductive activation of molecular oxygen. Full oxidation of methanol is achieved, generating three equivalents of hydrogen peroxide that can be used completely for the stereoselective hydroxylation of ethylbenzene as a model reaction. Overall we propose and demonstrate an atom-efficient and easily applicable alternative to established hydrogen peroxide generation methods, which enables the efficient use of peroxygenases for oxyfunctionalization reactions.

Original languageEnglish
Pages (from-to)798-801
JournalAngewandte Chemie-International Edition
Issue number2
Publication statusPublished - 2016


  • Heme proteins
  • Hydrogen peroxide
  • Hydroxylation
  • Oxidation
  • Peroxygenases

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