Chemical Equivalent of Arene Monooxygenases: Dearomative Synthesis of Arene Oxides and Oxepines
Chemical Equivalent of Arene Monooxygenases: Dearomative Synthesis of Arene Oxides and Oxepines
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DOI：
10.1021/jacs.0c02724
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发表时间：
2020-06-03
影响因子：
15
通讯作者：
Sarlah, David
中科院分区：
文献类型：
--
作者：
Siddiqi, Zohaib;Wertjes, William C.;Sarlah, David
细胞色素P450单加氧酶直接环氧化芳香环是真核生物芳烃代谢的主要途径之一。所得的芳烃氧化物用作酚类、氧杂环庚烯类或基于反式二氢二醇的代谢物的通用前体。虽然这些化合物具有重要的生物和化学相关性，但由于缺乏生产方法，妨碍了其利用。在这里，我们报告了一个通用的芳烃氧化物的脱芳构化合成的亲芳烃为基础的战略。该方法的温和性允许获得敏感的单环芳烃氧化物，而没有任何明显的酚类分解。此外，该方法能够将多环芳烃和杂芳烃直接转化为相应的氧杂环庚三烯。最后，这些研究提供了简单芳香族前体与复杂有机小分子之间通过芳烃氧化物和氧杂卓的直接联系。
Direct epoxidation of aromatic nuclei by cytochrome P450 monooxygenases is one of the major metabolic pathways of arenes in eukaryotes. The resulting arene oxides serve as versatile precursors to phenols, oxepines, or trans-dihydrodiol-based metabolites. Although such compounds have an important biological and chemical relevance, the lack of methods for their production has hampered access to their utility. Herein, we report a general arenophile-based strategy for the dearomative synthesis of arene oxides. The mildness of this method permits access to sensitive monocyclic arene oxides without any noticeable decomposition to phenols. Moreover, this method enables direct conversion of polycyclic arenes and heteroarenes into the corresponding oxepines. Finally, these studies provided direct connection between simple aromatic precursors and complex small organic molecules via arene oxides and oxepines.