Photochemically Driven Biocatalysis of Halogenases for the Green Production of Chlorinated Compounds
Photochemically Driven Biocatalysis of Halogenases for the Green Production of Chlorinated Compounds
复制标题
DOI：
10.1002/cctc.201800280
复制
发表时间：
2018-08
期刊：
影响因子：
4.5
通讯作者：
L. Schroeder;M. Frese;C. Müller;N. Sewald;T. Kottke
中科院分区：
文献类型：
--
作者：
L. Schroeder;M. Frese;C. Müller;N. Sewald;T. Kottke
依赖于黄素的色氨酸卤化酶在温和的条件下为氯化和溴化吲哚衍生物提供了一种区域选择性的途径。卤化酶的应用需要还原黄素辅因子FADH2的再生系统，这通常是通过酶或化学反应来实现的。以红孢链霉菌产生的卤代酶PYRH为模型体系，建立了利用蓝光和还原剂对FADH2进行光化学再生的方法。与以前使用黄素的光驱动生物催化不同，在我们的方法中，酶结合的黄素的转化抑制了无效的循环，在这个循环中，游离的黄素在产生过氧化氢的情况下与氧气反应。在25h内，70%的0.5 mM色氨酸区域选择性地转化为5-氯色氨酸。我们的再生系统为生产氯化化合物铺平了道路，只需在水溶液中使用光、卤化物盐、空气和廉价的牺牲电子给体。
Flavin‐dependent tryptophan halogenases provide a regioselective access to chlorinated and brominated indole derivatives under mild conditions. Application of the halogenase requires a regeneration system for the reduced flavin cofactor FADH2, which is usually achieved by enzymatic or chemical reactions. We employed the halogenase PyrH from Streptomyces rugosporus as a model system to establish a photochemical approach by using blue light and a reductant for regeneration of FADH2. In contrast to previous light‐driven biocatalysis using flavin, the conversion of enzyme‐bound flavin in our approach suppresses futile cycles, in which the free flavin reacts with oxygen under generation of H2O2. Within 25 h, 70 % of 0.5 mm tryptophan was converted regioselectively to 5‐chlorotryptophan. Our regeneration system paves the way for production of chlorinated compounds by applying only light, halide salt, air, and a cheap sacrificial electron donor in aqueous solution.