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Exploring the Substrate Specificity and Enantioselectivity of a Baeyer–Villiger Monooxygenase from Dietzia sp. D5: Oxidation of Sulfides and Aldehydes

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Abstract

Baeyer–Villiger monooxygenases (BVMOs) are valuable enzymes for specific oxyfunctionalization chemistry. They catalyze the oxidation of ketones to esters, but are also capable of oxidizing other chemical functions, namely aldehydes and heteroatoms such as sulfur, nitrogen, selenium and boron. The oxidation specificity and enantioselectivity of a newly characterized BVMO (BVMO4) from a strain of Dietzia towards sulfide- and aldehyde substrates have been studied. BVMO4 could react with sulfides containing an aromatic group. The presence of a substituent on the aromatic group was tolerated when they were in the meta- and para position and the oxidations yielded predominantly the (R)-sulfoxides. Similarly, BVMO4 displayed a higher activity for aldehydes containing a phenyl group, but long aliphatic aldehydes, namely octanal and decanal, were also accepted as substrate by this enzyme. The major oxidation products of the aldehyde substrates were the respective carboxylic acids in contrast to formate ester that was obtained in most of the previous reports. The Baeyer–Villiger oxidation of the substrate 2-phenylpropionaldehyde was studied in further detail and the corresponding acid product was obtained with good regio- and enantioselectivity. This is a unique feature for BVMO4 and is of great interest for further exploration of an alternative biocatalytic process.

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Acknowledgments

Marie Curie Networks for Initial Training fellowship in the project “BIOTRAINS” (FP7-PEOPLE-ITN-2008-238531) is acknowledged for funding. We would like to thank Maarten Gorseling and Remco van Oosten (Delft University) for technical assistance.

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Authors and Affiliations

  1. Department of Biotechnology, Center for Chemistry and Chemical Engineering, Lund University, P.O. Box 124, 221 00, Lund, Sweden

    Serena Bisagni, Rajni Hatti-Kaul & Gashaw Mamo

  2. Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK

    Benjamin Summers & Gideon Grogan

  3. Department of Biotechnology, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands

    Selin Kara & Frank Hollmann

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  1. Serena Bisagni
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  2. Benjamin Summers
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  3. Selin Kara
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  4. Rajni Hatti-Kaul
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  6. Gashaw Mamo
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  7. Frank Hollmann
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Correspondence to Serena Bisagni.

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Bisagni, S., Summers, B., Kara, S. et al. Exploring the Substrate Specificity and Enantioselectivity of a Baeyer–Villiger Monooxygenase from Dietzia sp. D5: Oxidation of Sulfides and Aldehydes. Top Catal 57, 366–375 (2014). https://doi.org/10.1007/s11244-013-0192-1

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