Engineering Rieske Non-Heme Iron Oxygenases for the Asymmetric Dihydroxylation of Alkenes
Engineering Rieske Non-Heme Iron Oxygenases for the Asymmetric Dihydroxylation of Alkenes
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DOI：
10.1002/anie.201506527
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发表时间：
2015-10-26
影响因子：
16.6
通讯作者：
Hauer, Bernhard
中科院分区：
文献类型：
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作者：
Gally, Christine;Nestl, Bettina M.;Hauer, Bernhard
烯烃的不对称二羟基化是特别有趣的，因为手性二醇产物很容易转化为有价值的衍生物。Rieske非血红素铁加氧酶（ROs）是一种很有前途的生物催化剂，因为它们可以有效地催化各种烯烃的选择性单羟基化和二羟基化。单点突变的引入提高了对选定烯烃的选择性（95%）和转化率（99%）。通过改变一个活性位点氨基酸侧链的大小，我们能够调节这些酶的区域选择性和立体选择性。对于不同的底物，与野生型ROs相比，突变体表现出改变的区域选择性，甚至倾向于相反的对映体，为各种结构不同的烯烃的氧化官能化提供了可持续的方法。
The asymmetric dihydroxylation of olefins is of special interest due to the facile transformation of the chiral diol products into valuable derivatives. Rieske non-heme iron oxygenases (ROs) represent promising biocatalysts for this reaction as they can be engineered to efficiently catalyze the selective mono- and dihydroxylation of various olefins. The introduction of a single point mutation improved selectivities (95%) and conversions (>99%) towards selected alkenes. By modifying the size of one active site amino acid side chain, we were able to modulate the regio- and stereoselectivity of these enzymes. For distinct substrates, mutants displayed altered regioselectivities or even favored opposite enantiomers compared to the wild-type ROs, offering a sustainable approach for the oxyfunctionalization of a wide variety of structurally different olefins.