Probing Unspecific Peroxygenases for Non‐Natural Nitrene Chemistry

Unspecific peroxygenases (UPOs) perform challenging oxyfunctionalization chemistry with high catalytic efficiency and reaction stability.[1‐5] In this report, we add nitrene chemistry to the current repertoire of UPO chemistry, utilizing the inexpensive commodity chemical hydroxylamine as co‐substrate. 1,2,3,4‐tetrahydronaphthalene was investigated as model substrate employing a diverse panel of UPOs, reaching turnover numbers up to 745 and enantiomeric excess values up to 62 %. Overall, we report the first account of UPO activity regarding non‐natural reactivities.