Enzymatic Epoxidation of Long-Chain Terminal Alkenes by Fungal Peroxygenases

Research output: Contribution to journalResearch articleContributedpeer-review



Terminal alkenes are among the most attractive starting materials for the synthesis of epoxides, which are essential and versatile intermediate building blocks for the pharmaceutical, fla-voring, and polymer industries. Previous research on alkene epoxidation has focused on the use of several oxidizing agents and/or different enzymes, including cytochrome P450 monooxygenases, as well as microbial whole-cell catalysts that have several drawbacks. Alternatively, we explored the ability of unspecific peroxygenases (UPOs) to selectively epoxidize terminal alkenes. UPOs are attractive biocatalysts because they are robust extracellular enzymes and only require H2O2 as cosub-strate. Here, we show how several UPOs, such as those from Cyclocybe (Agrocybe) aegerita (AaeUPO), Marasmius rotula (MroUPO), Coprinopsis cinerea (rCciUPO), Humicola insolens (rHinUPO), and Daldinia caldariorum (rDcaUPO), are able to catalyze the epoxidation of long-chain terminal alkenes (from C12:1 to C20:1) after an initial optimization of several reaction parameters (cosolvent, cosub-strate, and pH). In addition to terminal epoxides, alkenols and other hydroxylated derivatives of the alkenes were formed. Although all UPOs were able to convert and epoxidize the alkenes, nota-ble differences were observed between them, with rCciUPO being responsible for the highest sub-strate turnover and MroUPO being the most selective with respect to terminal epoxidation. The potential of peroxygenases for epoxidizing long-chain terminal alkenes represents an interesting and green alternative to the existing synthesis technologies.


Original languageEnglish
Article number522
Pages (from-to)1-12
Number of pages12
Issue number3
Publication statusPublished - 8 Mar 2022

External IDs

Scopus 85126026913
PubMed 35326172
WOS 000776839300001
Mendeley 32d81808-bb8b-3ff8-9297-73b3480338e9
unpaywall 10.3390/antiox11030522


DFG Classification of Subject Areas according to Review Boards


  • epoxidation, epoxides, oxyfunctionalization, peroxygenases, terminal alkenes

Library keywords