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Lipase-Mediated Selective Oxidation of Furfural and 5-Hydroxymethylfurfural

Authors

  • Monika Krystof,

    1. Institut für Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany), Fax: (+49) 241-8022177
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  • Dr. María Pérez-Sánchez,

    1. Institut für Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany), Fax: (+49) 241-8022177
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  • Dr. Pablo Domínguez de María

    Corresponding author
    1. Institut für Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany), Fax: (+49) 241-8022177
    • Institut für Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany), Fax: (+49) 241-8022177
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Abstract

Furfural and 5-hydroxymethylfurfural (HMF) are important biomass-derived platform chemicals that can be obtained from the dehydration of lignocellulosic sugars. A possible route for the derivatization of furanics is their oxidation to afford a broad range of chemicals with promising applications (e.g., diacids, hydroxyl acids, aldehyde acids, monomers for novel polymers). Herein we explore the organic peracid-assisted oxidation of furanics under mild reaction conditions. Using lipases as biocatalysts, alkyl esters as acyl donors, and aqueous solutions of hydrogen peroxide (30 % v/v) added stepwise, peracids are formed in situ, which subsequently oxidize the aldehyde groups to afford carboxylic acids with high yields and excellent selectivities. Furthermore, the use of an immobilized silica-based 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) affords the selective oxidation of the hydroxymethyl group of HMF to afford 2,5-diformylfuran. That product can be subsequently oxidized using again lipases for the in situ peracid formation to yield 2,5-furandicarboxylic acid, which is considered to be a key building block for biorefineries. These lipase-mediated reactions proceeded efficiently even with high substrate loadings under still non-optimized conditions. Overall, a proof-of-concept for the oxidation of furanics (based on in situ formed organic peracids as oxidants) is provided.

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