Dearomative dihydroxylation with arenophiles.
Dearomative dihydroxylation with arenophiles.
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DOI：
10.1038/nchem.2594
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发表时间：
2016-10
期刊：
影响因子：
21.8
通讯作者：
Sarlah D
中科院分区：
文献类型：
--
作者：
Southgate EH;Pospech J;Fu J;Holycross DR;Sarlah D
芳烃是一些最基本的原料化学品，每年以百万公吨的规模生产，并用于生产聚合物、油漆、农用化学品和药物。脱芳构化反应将简单的、容易获得的芳烃转化为具有更广泛潜在用途的更复杂的分子，然而，尽管在该领域中取得了实质性进展和成就，但用于简单芳烃的脱芳构化的方法相对较少，其也选择性地引入官能度。在这里，我们描述了一种新的脱芳构化过程，涉及可见光活化的小杂原子的有机分子arenophiles-这导致他们的对位环加成与各种芳香族化合物。该方法使用N-N-亲芳烃以使简单芳烃的脱芳二羟基化和二氨基二羟基化成为可能。该策略提供了直接和选择性地获得高度官能化的环己烯和环己二烯的途径，并且与现有的化学和生物脱芳构化方法正交。最后，我们展示了这种策略的合成效用与几种生物活性化合物和天然产物的简洁合成。
Aromatic hydrocarbons are some of the most elementary feedstock chemicals, produced annually on a million metric ton scale, and are used in the production of polymers, paints, agrochemicals and pharmaceuticals. Dearomatization reactions convert simple, readily available arenes into more complex molecules with broader potential utility, however, despite substantial progress and achievements in this field, there are relatively few methods for the dearomatization of simple arenes that also selectively introduce functionality. Here we describe a new dearomatization process that involves visible-light activation of small heteroatom-containing organic molecules—arenophiles—that results in their para-cycloaddition with a variety of aromatic compounds. The approach uses N–N-arenophiles to enable dearomative dihydroxylation and diaminodihydroxylation of simple arenes. This strategy provides direct and selective access to highly functionalized cyclohexenes and cyclohexadienes and is orthogonal to existing chemical and biological dearomatization processes. Finally, we demonstrate the synthetic utility of this strategy with the concise synthesis of several biologically active compounds and natural products.
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影响因子：
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