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Carbon-oxygen bond formation by fungal laccases: cross-coupling of 2,5-dihydroxy-N-(2-hydroxyethyl)-benzamide with the solvents water, methanol, and other alcohols

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Abstract

Laccase-catalyzed reactions lead to oxidation of the substrate via a cation radical, which has been described to undergo proton addition to form a quinonoid derivative or nucleophilic attack by itself producing homomolecular dimers. In this study, for the substrate 2,5-dihydroxy-N-(2-hydroxyethyl)-benzamide, we show that, besides the quinonoid form of substrate, all products formed are nonhomomolecular ones. Indeed, without addition of a reaction partner, heteromolecular products are formed from the quinonoid form of the laccase-substrate and the solvents water or methanol present in the incubation assay. Consequently, in laccase catalyzed syntheses performed in aqueous solutions or in the presence of methanol or other alcohols, undesirable heteromolecular coupling reactions between the laccase substrate and solvents must be taken into account. Additionally, it could be shown at the example of methanol and other alcohols that C-O-bound cross-coupling of dihydroxylated aromatic substances with the hydroxyl group of aliphatic alcohols can be catalyzed by fungal laccases.

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Acknowledgments

Financial support from the government of Mecklenburg-Vorpommern, Germany, and from the European Union (Landesforschungsschwerpunkt “Neue Wirkstoffe und Biomaterialien—Innovative Screeningverfahren and Produktentwicklung”) is gratefully acknowledged.

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Authors and Affiliations

  1. Institute for Microbiology, Ernst-Moritz-Arndt-University Greifswald, Friedrich-Ludwig-Jahn-Str. 15, 17487, Greifswald, Germany

    Katrin Manda, Annett Mikolasch & Frieder Schauer

  2. Institute of Automation, University of Rostock, Richard-Wagner-Str. 31, 18119, Rostock, Germany

    Dirk Gördes, Enrico Schmidt & Kerstin Thurow

  3. Laboratory for Functional Genomics, Ernst-Moritz-Arndt-University Greifswald, Walther-Rathenau-Str. 49a, 17489, Greifswald, Germany

    Elke Hammer

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  1. Katrin Manda
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  2. Dirk Gördes
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Correspondence to Katrin Manda.

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Manda, K., Gördes, D., Mikolasch, A. et al. Carbon-oxygen bond formation by fungal laccases: cross-coupling of 2,5-dihydroxy-N-(2-hydroxyethyl)-benzamide with the solvents water, methanol, and other alcohols. Appl Microbiol Biotechnol 76, 407–416 (2007). https://doi.org/10.1007/s00253-007-1024-7

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