关键词: biocatalysis enzymes oxidoreductases reduction stereoselectivity

来  源:   DOI:10.1002/cbic.202100445

Abstract:
Ene-reductases from the Old Yellow Enzyme (OYE) superfamily are a well-known and efficient biocatalytic alternative for the asymmetric reduction of C=C bonds. Considering the broad variety of substituents that can be tolerated, and the excellent stereoselectivities achieved, it is apparent why these enzymes are so appealing for preparative and industrial applications. Different classes of C=C bonds activated by at least one electron-withdrawing group have been shown to be accepted by these versatile biocatalysts in the last decades, affording a vast range of chiral intermediates employed in the synthesis of pharmaceuticals, agrochemicals, flavours, fragrances and fine chemicals. In order to access both enantiomers of reduced products, stereodivergent pairs of OYEs are desirable, but their natural occurrence is limited. The detailed knowledge of the stereochemical course of the reaction can uncover alternative strategies to orient the selectivity via mutagenesis, evolution, and substrate engineering. An overview of the ongoing studies on OYE-mediated bioreductions will be provided, with particular focus on stereochemical investigations by deuterium labelling.
摘要:
来自旧黄酶(OYE)超家族的烯还原酶是C=C键不对称还原的众所周知且有效的生物催化替代品。考虑到可以容忍的各种取代基,和获得的优异的立体选择性,很明显为什么这些酶对制备和工业应用如此有吸引力。在过去的几十年中,由至少一个吸电子基团活化的不同类型的C=C键已被这些多功能生物催化剂所接受。提供广泛的用于药物合成的手性中间体,农用化学品,风味,香料和精细化学品。为了获得还原产物的两种对映异构体,立体发散的OYE对是可取的,但它们的自然发生是有限的。对反应立体化学过程的详细了解可以揭示通过诱变定向选择性的替代策略,进化,和基底工程。将提供正在进行的OYE介导的生物还原研究的概述,特别关注通过氘标记进行的立体化学研究。
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