Heterogeneous Fe‐N‐C Cocatalyst for Hydroquinone Oxidation Enables Aerobic Oxidation of Primary Alcohols to Aldehydes

Asmaul Hoque, Md; Schweinzer, Clara; Martinez, Jesse J.; Tewes, Friederike; Sacchetti, Vittorio; Grützmacher, Hansjörg; Stahl, Shannon S.

doi:10.1002/anie.202424778

Title: Heterogeneous Fe‐N‐C Cocatalyst for Hydroquinone Oxidation Enables Aerobic Oxidation of Primary Alcohols to Aldehydes

Journal Article · 11 March 2025 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202424778 · OSTI ID:2530647

^[1]; Schweinzer, Clara ^[2]; Martinez, Jesse J. ^[1]; Tewes, Friederike ^[2]; Sacchetti, Vittorio ^[2];

^[2];

^[1]

Department of Chemistry University of Wisconsin-Madison Madison WI 53706 USA
Department of Chemistry and Applied Biosciences, ETH Zürich Vladimir-Prelog-Weg 1 8093Zürich Switzerland

Abstract Benzoquinone (BQ) is commonly used as a cocatalyst in multi‐component catalyst systems for aerobic oxidation of organic molecules. Such methods often proceed by a redox cascade in which a secondary catalyst supports aerobic oxidation of hydroquinone (HQ) to BQ. The present study shows that a commercially available non‐precious metal heterogeneous catalyst, PAJ‐Fe‐N‐C, is much more efficient than established homogeneous catalysts for aerobic oxidation of HQ to BQ, and this improved reactivity is crucial to support aerobic oxidation of primary alcohols to aldehydes with the homogeneous iridium catalyst, [Ir(trop ₂ DAD]OTf (trop ₂ DAD= N , N ‐bis(5‐ H ‐dibenzo[ a , d ]cycloheptene‐5‐yl)‐1,4‐diazabuta‐1,3‐diene). The combination of this heterogeneous/homogeneous catalyst system operates with Ir catalyst loadings as low as 0.05 mol % and turnover frequencies ≥350 h ⁻¹ .

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Research Organization:: University of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: Swiss National Science Foundation; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15690

OSTI ID:: 2530647

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition); ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Aerobic
alcohol oxidation
aldehydes
benzoquinone
catalysis

Title: Heterogeneous Fe‐N‐C Cocatalyst for Hydroquinone Oxidation Enables Aerobic Oxidation of Primary Alcohols to Aldehydes

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