Probing Unspecific Peroxygenases for Non‐Natural Nitrene Chemistry

Unspecific peroxygenases (UPOs) perform challenging oxyfunctionalization chemistry with high catalytic efficiency and reaction stability. In this report, nitrene chemistry to the current repertoire of UPO chemistry is added, utilizing the inexpensive commodity chemical hydroxylamine as cosubstrate. 1,2,3,4-tetrahydronaphthalene is investigated as model substrate using a diverse panel of UPOs, reaching turnover numbers up to 745 and enantiomeric excess values up to 62%. Overall, the first account of UPO activity regarding non-natural nitrene activities is reported.