Copper‐catalyzed monooxygenation of phenols: evidence for a mononuclear reaction mechanism

Abstract: The CuI salts [Cu(CH3CN)4]PF and [Cu(oDFB)2]PF with the very weakly coordinating anion Al(OC(CF3)3)4− (PF) as well as [Cu(NEt3)2]PF comprising the unique, linear bis-triethylamine complex [Cu(NEt3)2]+ were synthesized and examined as catalysts for the conversion of monophenols to o-quinones. The activities of these CuI salts towards monooxygenation of 2,4-di-tert-butylphenol (DTBP-H) were compared to those of [Cu(CH3CN)4]X salts with “classic” anions (BF4−, OTf−, PF6−), revealing an anion effect on the activity of the catalyst and a ligand effect on the reaction rate. The reaction is drastically accelerated by employing CuII-semiquinone complexes as catalysts, indicating that formation of a CuII complex precedes the actual catalytic cycle. This result and other experimental observations show that with these systems the oxygenation of monophenols does not follow a dinuclear, but a mononuclear pathway analogous to that of topaquinone cofactor biosynthesis in amine oxidase

Object Details

• Location: Deutsche Nationalbibliothek Frankfurt am Main
• Extent: Online-Ressource
• Language: Englisch
• Notes: Angewandte Chemie. International edition. - 61, 25 (2022) , ISSN: 1521-3773

Contributors, Places and Time

• Event: Veröffentlichung
• (where): Freiburg
• (who): Universität
• (when): 2022
• Creator: Schneider, Rebecca ; Engesser, Tobias Adrian ; Näther, Christian ; Krossing, Ingo ; Tuczek, Felix
• Contributor: Freiburger Material-Forschungszentrum ; Albert-Ludwigs-Universität Freiburg. Freiburger Zentrum für interaktive Werkstoffe und bioinspirierte Technologien ; Institut für Anorganische und Analytische Chemie. Freiburg im Breisgau

Further information

• DOI: 10.1002/anie.202202562
• URN: urn:nbn:de:bsz:25-freidok-2307408
• Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
• Last update: 15.08.2025, 7:26 AM CEST