Selective Oxyfunctionalisation Reactions Driven by Sulfite Oxidase-Catalysed In Situ Generation of H₂O₂

H₂O₂ can be accepted by several peroxygenases as a clean oxidant, able to supply both the necessary electrons and oxygen atom at the same time. The biocatalysts, in turn, are able to catalyse an array of interesting oxygen insertion reactions at enantio- and regio-selectivities hard to attain with classical chemical...

Chemoenzymatic Halocyclization of 4-Pentenoic Acid at Preparative Scale

The scale-up of chemoenzymatic bromolactonization to 100 g scale is presented, together with an identification of current limitations. The preparative-scale reaction also allowed for meaningful mass balances identifying current bottlenecks of the chemoenzymatic reaction.

FOx News: Towards Methanol-driven Biocatalytic Oxyfunctionalisation Reactions

The novel formate oxidase from Aspergillus oryzae (AoFOx) is a useful catalyst to promote H₂O₂-dependent oxyfunctionalisation reactions. In this contribution we exploit the substrate promiscuity of AoFOx to fully oxidise methanol and formaldehyde to CO₂ and drive peroxygenase-catalysed stereoselective...

Photochemical regeneration of flavoenzymes – An Old Yellow Enzyme case-study

Direct, NAD(P)H-independent regeneration of Old Yellow Enzymes represents an interesting approach for simplified reaction schemes for the stereoselective reduction of conjugated C=C-double bonds. Simply by illuminating the reaction mixtures with blue light in the presence of sacrificial electron donors enables to circumvent the costly and...

Cascading g-C₃N₄ and Peroxygenases for Selective Oxyfunctionalization Reactions

Peroxygenases are very interesting catalysts for specific oxyfunctionalization chemistry. Instead of relying on complicated electron transport chains, they rely on simple hydrogen peroxide as the stoichiometric oxidant. Their poor robustness against H₂O₂ can be addressed via in situ generation of H₂O<sub>2<...

Peroxygenase-Catalysed Epoxidation of Styrene Derivatives in Neat Reaction Media

Biocatalytic oxyfunctionalisation reactions are traditionally conducted in aqueous media limiting their production yield. Here we report the application of a peroxygenase in neat reaction conditions reaching product concentrations of up to 360 mM.

Photoenzymatic epoxidation of styrenes

Two-component-diffusible-flavomonooxygenases are versatile biocatalysts for selective epoxidation-, hydroxylation- or halogenation reactions. Their complicated molecular architecture can be simplified using photochemical regeneration of the catalytically active, reduced FADH ₂ prosthetic group. In this contribution we provide the...

Metals in Biotechnology: Cr-Driven Stereoselective Reduction of Conjugated C=C Double Bonds

Elemental metals are shown to be suitable sacrificial electron donors to drive the stereoselective reduction of conjugated C=C double bonds using Old Yellow Enzymes as catalysts. Both direct electron transfer from the metal to the enzyme as well as mediated electron transfer is feasible, although the latter excels by higher reaction rates....

Deazaflavins as photocatalysts for the direct reductive regeneration of flavoenzymes

Deazaflavins are potentially useful redox mediators for the direct, nicotinamide-independent regeneration of oxidoreductases. Especially the O₂-stability of their reduced forms have attracted significant interest for the regeneration of monooxygenases. In this contribution we further investigate the photochemical properties of...