Details zur Publikation

Kategorie Textpublikation
Referenztyp Zeitschriften
DOI 10.1002/cbic.201600677
Titel (primär) A peroxygenase from Chaetomium globosum catalyzes the selective oxygenation of testosterone
Autor Kiebist, J.; Schmidtke, K.-U.; Zimmermann, J.; Kellner, H.; Jehmlich, N.; Ullrich, R.; Zänder, D.; Hofrichter, M.; Scheibner, K.
Journal / Serie Chembiochem
Erscheinungsjahr 2017
Department MOLSYB
Band/Volume 18
Heft 6
Seite von 563
Seite bis 569
Sprache englisch
Keywords epoxidation; hydroxylation; oxyfunctionalization; peroxidase; steroid
UFZ Querschnittsthemen RU3;
Abstract Unspecific peroxygenases (UPO, EC secreted by fungi open an efficient way to selectively oxyfunctionalize diverse organic substrates, including less-activated hydrocarbons, by transferring peroxide-borne oxygen. We investigated a cell-free approach to incorporate epoxy and hydroxyl functionalities directly into the bulky molecule testosterone by a novel unspecific peroxygenase (UPO) that is produced by the ascomycetous fungus Chaetomium globosum in a complex medium rich in carbon and nitrogen. Purification by fast protein liquid chromatography revealed two enzyme fractions with the same molecular mass (36 kDa) and with specific activity of 4.4 to 12 U mg−1. Although the well-known UPOs of Agrocybe aegerita (AaeUPO) and Marasmius rotula (MroUPO) failed to convert testosterone in a comparative study, the UPO of C. globosum (CglUPO) accepted testosterone as substrate and converted it with total turnover number (TTN) of up to 7000 into two oxygenated products: the 4,5-epoxide of testosterone in β-configuration and 16α-hydroxytestosterone. The reaction performed on a 100 mg scale resulted in the formation of about 90 % of the epoxide and 10 % of the hydroxylation product, both of which could be isolated with purities above 96 %. Thus, CglUPO is a promising biocatalyst for the oxyfunctionalization of bulky steroids and it will be a useful tool for the synthesis of pharmaceutically relevant steroidal molecules.
dauerhafte UFZ-Verlinkung
Kiebist, J., Schmidtke, K.-U., Zimmermann, J., Kellner, H., Jehmlich, N., Ullrich, R., Zänder, D., Hofrichter, M., Scheibner, K. (2017):
A peroxygenase from Chaetomium globosum catalyzes the selective oxygenation of testosterone
ChemBioChem 18 (6), 563 - 569