Publication Details

Category Text Publication
Reference Category Journals
DOI 10.1002/cbic.201600677
Title (Primary) A peroxygenase from Chaetomium globosum catalyzes the selective oxygenation of testosterone
Author Kiebist, J.; Schmidtke, K.-U.; Zimmermann, J.; Kellner, H.; Jehmlich, N. ORCID logo ; Ullrich, R.; Zänder, D.; Hofrichter, M.; Scheibner, K.
Source Titel Chembiochem
Year 2017
Department MOLSYB
Volume 18
Issue 6
Page From 563
Page To 569
Language englisch
Keywords epoxidation; hydroxylation; oxyfunctionalization; peroxidase; steroid
UFZ wide themes 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.
Persistent UFZ Identifier
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 10.1002/cbic.201600677