Complementary Oxidations of Agrochemicals and Intermediates by Class I and II Unspecific Peroxygenases

Selective oxidation reactions can be a useful tool in the generation of metabolites of bioactive compounds for analytical and toxicology studies. In this study we show that a range of commonly encountered agrochemicals and synthetic intermediates can be selectively oxidised to form valuable precursors and metabolite compounds using the complementary activities of Class I and Class II unspecific peroxygenases (UPOs) on preparative scale, permitting full product characterisation. In this way, several UPO-mediated biotransformations of agrochemically relevant intermediates have been uncovered; these include the hydroxylation of phenylureas and isoxazolidinones and the N-dealkylation of triazines. Hence the herbicide clomazone was hydroxylated by the Class I artUPO to give 5-hydroxyclomazone in 27% isoltaed yield, but was not transformed by the Class II UPO rAaeUPO-PaDa-I-H. However, the Class II UPO could be used to transform isoproturon to to give the hydroxylated product 2-hydroxy-IPU with 57% isolated yield.