The selective enzymatic reduction of nitroaliphatic and nitroaromatic compounds to aliphatic amines and amino-, azoxy- and azo-aromatics, respectively, remains a persisting challenge for biocatalysis. Here we demonstrate the light-powered, selective photoenzymatic synthesis of aliphatic amines and amino-, azoxy- and azo-aromatics from the corresponding nitro compounds. The nitroreductase from Bacillus amyloliquefaciens, in synergy with a photocatalytic system based on chlorophyll, promotes selective conversions of electronically-diverse nitroarenes into a series of aromatic amino, azoxy and azo products with excellent yield (up to 97%). The exploitation of an alternative nitroreductase from Enterobacter cloacae enables the tailoring of a photoenzymatic system for the challenging synthesis of aliphatic amines from nitroalkenes and nitroalkanes (up to 90% yield). This photoenzymatic reduction overcomes the competing bio-Nef reaction, typically hindering the complete enzymatic reduction of nitroaliphatics. The results highlight the usefulness of nitroreductases to create selective photoenzymatic systems for the synthesis of precious chemicals, and the effectiveness of chlorophyll as an innocuous photocatalyst, enabling the use of sunlight to drive the photobiocatalytic reactions.

硝基脂肪族和硝基芳香族化合物分别选择性酶促还原为脂肪胺和氨基、氧化偶氮和偶氮芳香族化合物仍然是生物催化领域持续存在的挑战。在这里，我们展示了从相应的硝基化合物中以光为动力、选择性光酶法合成脂肪胺以及氨基、氧化偶氮和偶氮芳香族化合物。来自解淀粉芽孢杆菌的硝基还原酶与基于叶绿素的光催化系统协同作用，促进电子多样化的硝基芳烃选择性转化为一系列芳香氨基、氧化偶氮和偶氮产物，且产率优异（高达 97%）。利用来自阴沟肠杆菌的替代硝基还原酶，可以定制光酶系统，用于从硝基烯烃和硝基烷烃合成脂肪胺的挑战性合成（产率高达 90%）。这种光酶还原克服了竞争性生物 Nef 反应，通常会阻碍硝基脂肪族化合物的完全酶还原。结果强调了硝基还原酶在创建用于合成贵重化学品的选择性光酶系统方面的有用性，以及叶绿素作为无害光催化剂的有效性，使得能够利用阳光来驱动光生物催化反应。