Force feeding PaDa-I: a hybrid nest for selective chemo-enzymatic oxyfunctionalization
(2026) Netherlands’ Catalysis and Chemistry Conference 2026 — Location: Noordwijkerhout, Pays-Bas (2.March.2026)
Files
NCCCXXVIIabstract.pdf
Open Access - Adobe PDF
- 702.02 KB
Details
- Authors
- Abstract
- In biocatalysis, unspecific peroxygenases (UPO) are a promising class of enzymes. They enable regio-and-enantioselective oxyfunctionalizations with minimal hydrogen peroxide, without needing additional cofactors1. However, adding excessive H2O2 externally can denature the enzyme, and the industrial, high-grade production of hydrogen peroxide is highly energy intensive. Thankfully, H2O2 can be produced in situ by gold-palladium catalysts at room temperature in water under low H2 pressure. Freakley et al. recently showed that combining Au-Pd catalysts with UPO enables one-pot cascade reactions without interference between catalysts.2 Learning from their work, and leaning on our group’s experience in the fabrication of chemo-enzymatic heterogeneous catalysts (HCEHC)3,4 we recreated those Au-Pd catalysts and combined them with a commercially available UPO (PaDa-I) in a single solid material. The resulting HCEHC, produced through an “enzyme-in-a-cage” strategy, was shown to be reusable and highly stereo-and regioselective for the hydroxylation of ethylbenzene to (R)-phenylethanol. Working in an acetone-rich reaction medium, a single gram per liter of our most active HCEHC manages the full conversion of 14mM of ethylbenzene into (R)-phenylethanol in less than 4 hours. This activity is on par with the free enzyme but allows for its recovery and reuse in a high atom-economy, one-pot, one-step chemo-enzymatic cascade reaction. In this work, we explore the effects of synthesis and operational parameters on both the activity of the catalysts and the quality of immobilization, as we search for a subtle balance between activity and robustness. 1. Hobisch, M. et al. Recent developments in the use of peroxygenases – Exploring their high potential in selective oxyfunctionalisations. Biotechnology Advances 51, 107615 (2021). 2. Freakley, S. J. et al. A chemo-enzymatic oxidation cascade to activate C–H bonds with in situ generated H2O2. Nat Commun 10, 4178 (2019). 3. Smeets, V. et al. Hollow zeolite microspheres as a nest for enzymes: a new route to hybrid heterogeneous catalysts. Chem. Sci. 11, 954–961 (2020). 4. Debecker, D. P. et al. Hybrid chemoenzymatic heterogeneous catalysts. Current Opinion in Green and Sustainable Chemistry 28, 100437 (2021).
- Affiliations
Citations
Kinnaer, M., & Debecker, D. (2026). Force feeding PaDa-I: a hybrid nest for selective chemo-enzymatic oxyfunctionalization. Netherlands’ Catalysis and Chemistry Conference 2026, Noordwijkerhout, Pays-Bas. https://hdl.handle.net/2078.5/273262