College of Life Sciences, Henan Agricultural University, 95 Wenhua Road, Zhengzhou, 450002, China.
College of Biological Engineering, Henan University of Technology, 100 Lianhua Street, Zhengzhou, 450001, China.
Angew Chem Int Ed Engl. 2022 Aug 8;61(32):e202206472. doi: 10.1002/anie.202206472. Epub 2022 Jun 21.
The addition of water to alkenes is an important method for the synthesis of alcohols, but the regioselectivity of acid-catalyzed hydration of terminal alkenes yields secondary alcohols according to Markovnikov's rule, making it difficult to obtain primary alcohols. Here we report a styrene monooxygenase that catalyzes the anti-Markovnikov hydration of the terminal aryl alkenes under anaerobic conditions. This hydration provides primary alcohols in good yields (up to 100 %), excellent anti-Markovnikov regioselectivity (>99 : 1), and good enantiomeric purity (60-83 % ee). Residues Asn46, Asp100, and Asn309 are essential for catalysis suggesting an acid-base mechanism with a carbanion-like intermediate that could account for the anti-Markovnikov regioselectivity. Our work reveals a new enzymatic tool with unusual regioselectivity based on the promiscuous catalytic activity of a monooxygenase.
烯烃加水是合成醇的重要方法，但酸催化的末端烯烃水合的区域选择性根据马氏规则生成仲醇，难以获得伯醇。在这里，我们报告了一种单加氧酶，它可以在厌氧条件下催化末端芳基烯烃的反马氏规则水合。这种水合作用以良好的收率（高达 100%）、优异的反马氏规则区域选择性（>99:1）和良好的对映体纯度（60-83%ee）提供伯醇。残基 Asn46、Asp100 和 Asn309 对于催化是必需的，这表明存在酸-碱机制，其中涉及碳负离子样中间体，这可以解释反马氏规则的区域选择性。我们的工作揭示了一种基于单加氧酶的混杂催化活性的具有不寻常区域选择性的新酶学工具。
