Chirality plays a significant role in the manufacture of pharmaceuticals and fine chemicals. The use of chemical catalysts to control stereoselectivity relies on the use of chiral catalysts with labor–intensive synthesis and purification. Natural enzymes offer inherent stereoselectivity, making them attractive catalysts for this purpose. We report here chiral biocatalytic oxidations in microemulsions driven by horseradish peroxidase coupled with a synthetic Cu2+‐polymer catalyst. This hybrid system features crosslinked layer–by–layer (LBL) films composed of polyions with Cu2+‐containing pyrene–labelled poly(2‐hydroxy‐3‐dipicolylamino) propyl methacrylate (Py−PGMADPA) to drive oxygen reduction to form hydrogen peroxide. Peroxide in turn activates horseradish peroxidase (HRP) crosslinked in LbL films on magnetic particle beads to biocatalytically oxidize styrene, ethylbenzene, and methyl phenylacetate to chiral products. R‐stereoisomers of these reactants were selectively formed with a high enantiomeric excess of ≥80 % at 90 °C. The enzyme films show high thermal stability at 90 °C in cetyltrimethylammonium bromide microemulsion. Reactions at 90 °C were essentially complete in 2 hr. This hybrid approach opens a door to new designs of biocatalytic syntheses using a separate electrocatalyst for enzyme activation.

中文翻译：

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电催化氧还原成过氧化氢驱动的微乳液中 90 °C 的手性生物催化氧化

手性在药品和精细化学品的制造中发挥着重要作用。使用化学催化剂来控制立体选择性依赖于手性催化剂的使用以及劳动密集型的合成和纯化。天然酶具有固有的立体选择性，使其成为用于此目的的有吸引力的催化剂。我们在此报告了由辣根过氧化物酶与合成铜驱动的微乳液中的手性生物催化氧化2+‐聚合物催化剂。该混合系统具有由聚离子和 Cu 组成的交联层层 (LBL) 薄膜2+含有芘标记的聚（2-羟基-3-二吡啶氨基）甲基丙烯酸丙酯（Py-PGMADPA）驱动氧还原形成过氧化氢。过氧化物反过来激活磁性颗粒珠上 LbL 膜中交联的辣根过氧化物酶 (HRP)，以生物催化方式将苯乙烯、乙苯和苯乙酸甲酯氧化成手性产物。这些反应物的 R 立体异构体在 90°C 时选择性地形成，对映体过量高达 ≥80%。酶膜在十六烷基三甲基溴化铵微乳液中在 90 °C 下表现出高热稳定性。 90°C 下的反应在 2 小时内基本完成。这种混合方法为使用单独的电催化剂进行酶激活的生物催化合成新设计打开了大门。