Genetically encodable photosensitizers allows for the design of artificial photoenzymes to expand the scope of abiological reactions. Here, we report the genetic incorporation of a thioxanthone‐containing amino acid into a protein scaffold using an engineered pyrrolysyl‐tRNA/pyrrolysyl‐tRNA synthetase pair. The designer enzyme was engineered to catalyze a dearomative [2 + 2] cycloaddition reaction in high yields (up to > 99% yield) with excellent enantioselectivity (up to 98:2 e.r.). This work provides a robust and facile method for photoenzyme design and lays the foundation for the development of photoenzymatic reactions.

中文翻译：

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含噻杂蒽醌的氨基酸的基因掺入用于人工光酶的设计


基因可编码的光敏剂允许设计人工光酶以扩大非生物反应的范围。在这里，我们报道了使用工程化的吡咯赖斯基-tRNA/吡咯赖斯基-tRNA 合成酶对将含有噻氧杂蒽酮的氨基酸遗传掺入蛋白质支架的过程。设计酶经过工程改造，可催化高产率（高达 > 99% 产量）的脱激 [2 + 2] 环加成反应，具有优异的对映选择性（高达 98：2 e.r.）。这项工作为光酶设计提供了一种稳健而简单的方法，为光酶反应的发展奠定了基础。