Arenophile-Mediated Photochemical Dearomatization of Nonactivated Arenes
Arenophile-Mediated Photochemical Dearomatization of Nonactivated Arenes
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DOI：
10.2533/chimia.2020.577
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发表时间：
2020-01-01
期刊：
影响因子：
1.2
通讯作者：
Sarlah, David
中科院分区：
文献类型：
--
作者：
Okumura, Mikiko;Sarlah, David
芳香族化合物是有机分子中含量最丰富的一类，可用作脂环烃的前体。虽然许多已建立的脱芳构化反应都非常强大，但同时引入官能化的脱芳构化，即脱芳烃功能化，仍然是一个很不发达的领域。本文综述了近年来利用亲芳烃-芳烃环加成平台对简单芳烃和非活化芳烃进行脱芳官能化的研究进展。这些通过可见光介导的[4+2]-光环加成反应形成的环加成物，可以通过烯烃化学或过渡金属催化的碳基、氮基和氧基亲核试剂的开环反应进行原位阐述，提供了获得具有功能和立体化学复杂性的不同结构的途径。此外，脱芳烃产品可以进一步细化，有效地将其他官能团安装到生成的脂环碳环上。亲芳烃介导的脱芳构化方法的实用性也因天然产物和生物活性化合物通过新的断链而容易合成而得到强调。
Aromatic compounds are one of the most abundant classes of organic molecules and find utility as precursors for alicyclic hydrocarbon building blocks. While many established dearomatization reactions are exceptionally powerful, dearomatization with concurrent introduction of functionality, i.e. dearomative functionalization, is still a largely underdeveloped field. This review aims to provide an overview of our recent efforts and progress in the development of dearomative functionalization of simple and nonactivated arenes using arenophile-arene cycloaddition platform. These cycloadducts, formed via a visible-light-mediated [4+2]-photocycloaddition, can be elaborated in situ through olefin chemistry or transition-metal-catalyzed ring-opening with carbon-, nitrogen-, and oxygen-based nucleophiles, providing access to diverse structures with functional and stereochemical complexity. Moreover, the dearomatized products are amenable to further elaborations, which effectively install other functionalities onto the resulting alicyclic carbocycles. The utility of the arenophile-mediated dearomatization methods are also highlighted by the facile syntheses of natural products and bioactive compounds through novel disconnections.