In this chapter the catalytic and structural properties of the vanadium chloroperoxidases will be discussed with an emphasis on their superb activity and stability under operational conditions. These properties make these enzymes attractive catalysts in organic synthesis and allow a number of applications. Some of the more recent findings are highlighted, e.g., the use of vanadium chloroperoxidase (VCPO) in the formation of singlet oxygen, halogenation of phenols, alkenes, halocyclisation of ϵ,γ-unsaturated alcohols and the aza-Achmatowicz reaction.

Peroxygenases offer an attractive means to address challenges in selective oxyfunctionalization chemistry. Despite this, their application in synthetic chemistry remains challenging due to their facile inactivation by the stoichiometric oxidant H₂O₂. Often atom-inefficient peroxide generation systems are required, which show little potential for large-scale implementation. Here, we show that visible-light-driven, catalytic water oxidation can be used for in situ generation of H₂O₂ from water, rendering the peroxygenase catalytically active. In this way, the stereoselective oxyfunctionalization of hydrocarbons can be achieved by simply using the catalytic system, water and visible light.

A catalytic, enzyme-initiated (aza-) Achmatowicz reaction is presented. The involvement of a robust vanadium-dependent peroxidase from Curvularia inaequalis allows the simple use of H₂O₂ and catalytic amounts of bromide.