Fungal Peroxygenases – A Versatile Tool for Biocatalysis

Unspecific peroxygenases (UPOs, EC 1.11.2.1) represent an enzyme type that exclusively occurs in the "Kingdom of fungi" including all larger phyla of Eumycota (true fungi) and pseudofungal Peronosporomycetes ("Oomycetes"). They are secreted heme-thiolate proteins that use hydrogen peroxide as electron acceptor and O-donor to catalyze diverse monooxygenations including sp3-carbon hydroxylations, sp2-epoxidations and heteroatom oxidations. Many of these oxyfunctionalizations proceed selectively and hence, bear an intriguing application potential in organic synthesis and other fields. Here, we provide an overview on fungal UPOs covering about 15 years of research with focus on their molecular, structural, catalytic and synthetic properties.