Repurposing Iron‐ and 2‐Oxoglutarate‐Dependent Oxygenases to Catalyze Olefin Hydration
Repurposing Iron‐ and 2‐Oxoglutarate‐Dependent Oxygenases to Catalyze Olefin Hydration
复制标题
重新利用铁和 2-氧戊二酸-依赖性氧化酶来催化烯烃水合
DOI：
10.1002/anie.202311099
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Chen, Chuo
中科院分区：
文献类型：
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作者：
Wang, Bingnan;Lu, Yong;Cha, Lide;Chen, Tzu‐Yu;Palacios, Philip M.;Li, Liping;Guo, Yisong;Chang, Wei‐chen;Chen, Chuo
已知单核血红素铁（II）和2-酮戊二酸（Fe/2 OG）依赖性加氧酶和卤化酶催化多种氧化反应，包括初级代谢和天然产物成熟中的羟基化、卤化、环氧化和去饱和。然而，它们在非生物转化中的应用主要限于C-H氧化。在此，我们表明，这个家庭的各种酶，当与Fe（II）或Fe（III）重组，可以催化Mukaiyama水合氧化还原中性转化。与Fe/2 OG酶的天然反应不同，其中涉及由铁氧物种催化的氧原子转移（OAT），这种非天然转化以2 OG非依赖性方式通过氢原子转移（HAT）途径进行。此外，与其中双核铁物质负责HAT的常规无机催化剂相反，Fe/2 OG酶利用单核铁中心来支持该反应。总的来说，我们的工作表明，Fe/2 OG酶在催化中的效用超出了目前的催化氧化范围。
Mononuclear nonheme iron(II) and 2‐oxoglutarate (Fe/2OG)‐dependent oxygenases and halogenases are known to catalyze a diverse set of oxidative reactions, including hydroxylation, halogenation, epoxidation, and desaturation in primary metabolism and natural product maturation. However, their use in abiotic transformations has mainly been limited to C−H oxidation. Herein, we show that various enzymes of this family, when reconstituted with Fe(II) or Fe(III), can catalyze Mukaiyama hydration—a redox neutral transformation. Distinct from the native reactions of the Fe/2OG enzymes, wherein oxygen atom transfer (OAT) catalyzed by an iron‐oxo species is involved, this nonnative transformation proceeds through a hydrogen atom transfer (HAT) pathway in a 2OG‐independent manner. Additionally, in contrast to conventional inorganic catalysts, wherein a dinuclear iron species is responsible for HAT, the Fe/2OG enzymes exploit a mononuclear iron center to support this reaction. Collectively, our work demonstrates that Fe/2OG enzymes have utility in catalysis beyond the current scope of catalytic oxidation.