一种工程化胆固醇氧化酶催化非甾体仲醇的对映选择性氧化。
An Engineered Cholesterol Oxidase Catalyses Enantioselective Oxidation of Non-steroidal Secondary Alcohols.
作者信息
Heath Rachel S, Sangster Jack J, Turner Nicholas J
机构信息
Department of Chemistry, University of Manchester, Manchester Institute of Biotechnology, 131 Princess Street, M1 7DN, Manchester, UK.
出版信息
Chembiochem. 2022 Apr 5;23(7):e202200075. doi: 10.1002/cbic.202200075. Epub 2022 Feb 22.
The enantioselective oxidation of 2° alcohols to ketones is an important reaction in synthetic chemistry, especially if it can be achieved using O -driven alcohol oxidases under mild reaction conditions. However to date, oxidation of secondary alcohols using alcohol oxidases has focused on activated benzylic or allylic substrates, with unactivated secondary alcohols showing poor activity. Here we show that cholesterol oxidase (EC 1.1.3.6) could be engineered for activity towards a range of aliphatic, cyclic, acyclic, allylic and benzylic secondary alcohols. Additionally, since the variants demonstrated high (S)-selectivity, deracemisation reactions were performed in the presence of ammonia borane to obtain enantiopure (R)-alcohols.
将仲醇对映选择性氧化为酮是合成化学中的一个重要反应，特别是如果能在温和的反应条件下使用以氧为驱动力的醇氧化酶来实现的话。然而，迄今为止，利用醇氧化酶对仲醇的氧化作用主要集中在活性苄基或烯丙基底物上，未活化的仲醇表现出较差的活性。在此我们表明，胆固醇氧化酶（EC 1.1.3.6）可以通过改造使其对一系列脂肪族、环状、非环状、烯丙基和苄基仲醇具有活性。此外，由于这些变体表现出高（S）-选择性，因此在氨硼烷存在的情况下进行了去消旋反应，以获得对映体纯的（R）-醇。
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