Key Laboratory of Engineering Biology for Low-carbon Manufacturing, Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, 32 West 7th Avenue, Tianjin, 300308, China.
School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, 710049, China.
Nat Commun. 2024 Sep 27;15(1):8312. doi: 10.1038/s41467-024-52648-0.
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) 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) form the desired azoxy products. This work expands the reactivity repertoire of biocatalytic transformations in the underexplored field of azoxy compound formation reactions.
酶在化学合成中正在产生重大影响。然而，与有机合成中可能的大量产品相比，通过生物催化可实现的化学产品范围仍然有限。例如，很少有使用酶催化剂合成偶氮产品。在这项研究中，我们发现真菌非特异性过氧化物酶是一种很有前途的催化剂，可以从简单的苯胺起始原料合成偶氮产品。催化特性（高达 48450 次转化和 6.7s 的转化频率）和底物转化（高达 99%的转化率和 98%的化学选择性）突出了其合成潜力。我们提出了一种机制，其中过氧化物酶衍生的羟胺和亚硝基化合物自发（非酶促）形成所需的偶氮产品。这项工作扩展了在偶氮化合物形成反应这一研究不足的领域中生物催化转化的反应谱。
