biostudies-literatureUnknown15(1)Li HEnzymes are making a significant impact on chemical synthesis. However, the range of chemical products achievable through biocatalysis is still limited compared to the vast array of products possible with organic synthesis. For instance, azoxy products have rarely been synthesized using enzyme catalysts. In this study, we discovered that fungal unspecific peroxygenases are promising catalysts for synthesizing azoxy products from simple aniline starting materials. The catalytic features (up to 48,450 turnovers and a turnover frequency of 6.7 s^-1) and substrate transformations (up to 99% conversion with 98% chemoselectivity) highlight the synthetic potential. We propose a mechanism where peroxygenase-derived hydroxylamine and nitroso compounds spontaneously (non-enzymatically) forNature communications8312https://www.ebi.ac.uk/biostudies/studies/S-EPMC11436639biostudies-literatureUnspecific peroxygenase enabled formation of azoxy compounds.PMC11436639Zhang WLi HSheng XHuang YDuan PZhang XZeng ZChen FShi JSu HHollmann FWu XfalseUnspecific peroxygenase enabled formation of azoxy compounds.Enzymes are making a significant impact on chemical synthesis. However, the range of chemical products achievable through biocatalysis is still limited compared to the vast array of products possible with organic synthesis. For instance, azoxy products have rarely been synthesized using enzyme catalysts. In this study, we discovered that fungal unspecific peroxygenases are promising catalysts for synthesizing azoxy products from simple aniline starting materials. The catalytic features (up to 48,450 turnovers and a turnover frequency of 6.7 s^-1) and substrate transformations (up to 99% conversion with 98% chemoselectivity) highlight the synthetic potential. We propose a mechanism where peroxygenase-derived hydroxylamine and nitroso compounds spontaneously (non-enzymatically) for2024-01-01T00:00:00Z2024 Sep2026-06-02T22:21:52.563Z2025-04-06T12:29:45.018ZS-EPMC114366393933313010.1038/s41467-024-52648-0