Formate Oxidase (FOx) from Aspergillus oryzae: One Catalyst Enables Diverse H₂O₂‐Dependent Biocatalytic Oxidation Reactions

Abstract

An increasing number of biocatalytic oxidation reactions rely on H 2 O 2 as a clean oxidant. The poor robustness of most enzymes towards H 2 O 2 , however, necessitates more efficient systems for in situ H 2 O 2 generation. In analogy to the well‐known formate dehydrogenase to promote NADH‐dependent reactions, we here propose employing formate oxidase (FOx) to promote H 2 O 2 ‐dependent enzymatic oxidation reactions. Even under non‐optimised conditions, high turnover numbers for coupled FOx/peroxygenase catalysis were achieved.

Haloperoxidases as catalysts in organic synthesis

“…66 Starting from γ,δ-unsaturated acids the corresponding halogenated butyrolactones are accessible (Scheme 8). 48 Interestingly, the high water solubility of the substrate also enabled higher reagent payloads.…”

A chemo-enzymatic oxidation cascade to activate C–H bonds with in situ generated H2O2

“…Additionally, the production of gluconic acid in the same reaction vessel as the UPOs necessitates continuous pH control to maintain the activity of the UPOs. A recently described formate oxidase, Ao FOx from Aspergillus oryzae , which uses sodium formate as source of reducing equivalents to produce H 2 O 2 , promises a significant improvement on GOX in terms of side product production, but still requires acid titration to maintain a constant pH 14 .…”

Biocatalyzed Redox Processes Employing Green Reaction Media

“…However, the dosage of H 2 O 2 is one of the limiting factors in the peroxygenase-catalyzed reactions, since a high concentration of this oxidant can inactivate the biocatalysts. For that reason, the peroxide needs to be continuously supplied or in situ generated to keep its concentration in limits enough to get a good activity without negative impact in their stability [ 50 , 51 ]. UPOs present also the advantage of being able to work with organic peroxides as co-substrates, thus expanding their catalysis to non-aqueous reaction media.…”