Cyclopropanation reactions by a class I unspecific peroxygenase
Jiacheng Li1, Katy A S Cornish1,2, Balázs Pogrányi1
1Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK. william.unsworth@york.ac.uk.
Organic & Biomolecular Chemistry
|April 30, 2025
Summary
Class I unspecific peroxygenases (UPOs) can now perform non-natural alkene cyclopropanation reactions. ArtUPO demonstrates diastereoselective and enantioselective cyclopropanation of styrenes, expanding UPO catalytic capabilities.
Area of Science:
- Biocatalysis
- Enzymology
- Organic Chemistry
Background:
- Hemoproteins like cytochrome P450 and myoglobin catalyze non-natural biotransformations, including alkene cyclopropanation via carbene insertion.
- Unspecific peroxygenases (UPOs) have not been previously explored for these cyclopropanation reactions.
Purpose of the Study:
- To investigate the potential of unspecific peroxygenases (UPOs) in catalyzing non-natural alkene cyclopropanation reactions.
- To determine if class I UPOs can perform diastereoselective and enantioselective cyclopropanation.
Main Methods:
- Utilized the class I enzyme ArtUPO for biotransformation studies.
- Employed styrenes and ethyldiazoacetate as substrates for the cyclopropanation reaction.
Main Results:
- Demonstrated that ArtUPO can perform alkene cyclopropanation.
- Achieved high diastereoselectivity and enantioselectivity in the cyclopropanation of styrenes with ethyldiazoacetate.
- Established a novel non-natural biotransformation for UPOs.
Conclusions:
- Class I UPOs, specifically ArtUPO, are capable of catalyzing alkene cyclopropanation reactions.
- This study expands the known catalytic repertoire of UPOs into non-natural biotransformations.
- ArtUPO represents a promising biocatalyst for stereoselective cyclopropanation reactions.
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