Catalytic enantioselective syn hydration of enones in water using a DNA-based catalyst
Catalytic enantioselective syn hydration of enones in water using a DNA-based catalyst
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DOI：
10.1038/nchem.819
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发表时间：
2010-11-01
期刊：
影响因子：
21.8
通讯作者：
Roelfes, Gerard
中科院分区：
文献类型：
--
作者：
Boersma, Arnold J.;Coquiere, David;Roelfes, Gerard
水对烯烃的对映选择性加成反应是生物体系中常见的反应，但这超出了合成化学家的能力。在这里，我们提出了第一个非酶催化对映体选择性水合烯酮的例子，为此我们使用了包含铜配合物的催化剂，该铜配合物基于非手性配体，非共价结合于（脱氧）核糖核酸，这是唯一的来源反应条件下存在的手性。获得了高达82%对映体过量的手性β-羟基酮产物。氘标记的研究表明，该反应是非对映体特异性的，只有syn水合产物形成。迄今为止，这种非对映体特异性和对映体选择性的反应在传统的均相催化中还没有等价物。
The enantioselective addition of water to olefins in an aqueous environment is a common transformation in biological systems, but was beyond the ability of synthetic chemists. Here, we present the first examples of a non-enzymatic catalytic enantioselective hydration of enones, for which we used a catalyst that comprises a copper complex, based on an achiral ligand, non-covalently bound to (deoxy)ribonucleic acid, which is the only source of chirality present under the reaction conditions. The chiral beta-hydroxy ketone product was obtained in up to 82% enantiomeric excess. Deuterium-labelling studies demonstrated that the reaction is diastereospecific, with only the syn hydration product formed. So far, this diastereospecific and enantioselective reaction had no equivalent in conventional homogeneous catalysis.