Mapping Selective Oxidations of Unspecific Peroxygenases

Several unspecific peroxygenases (UPOs) have been identified that perform a broad range of selective oxyfunctionalizations and hence represent a pivotal addition to the biocatalysis 'toolbox'. To make these 'oxidation tools' broadly applicable it is crucial to provide a detailed 'user manual' for their substrate preference, chemo- and regioselectivity. We therefore selected 16 different substrates with a panel of 15 diverse UPOs and mapped their preferences. Various UPOs proved to be highly selective - discriminating based on either position or chemical properties of the substrate - with up to 99 % chemo- and regioselectivity while achieving turnover numbers (TONs) of a few hundred up to multiple thousands. This map of UPO selectivity shall serve as a starting point for new chemoenzymatic routes and starting points for protein engineering endeavors.