Arynes offer immense potential for diversification of benzenoid rings, which occur in pharmaceuticals, agrochemicals, and liquid crystals. However, accessing these high-energy intermediates requires synthetic precursors, which involve either harsh conditions or multistep syntheses. The development of alternative methods to access arynes using simpler substrates and milder conditions is necessary for a more streamlined approach. Here, we describe a two-step formal dehydrogenation of simple arenes to generate arynes at a remote position relative to traditionally reactive groups, e.g., halides. This approach is enabled by regioselective installation and ejection of an “onium” leaving group, and we demonstrate the compatibility of simple arenes (20 examples) and arynophiles (8 examples). Moreover, through direct comparison, we show that our formal dehydrogenation method is both more functional group tolerant and efficient in generating arynes than the current state-of-the-art aryne precursors. Finally, we show that aryne intermediates offer opportunities for regioselective C–H amination that are distinct from other methods.

中文翻译：

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芳烃形式脱氢合成芳烃

芳烃为苯环化合物的多样化提供了巨大的潜力，苯环化合物存在于药物、农用化学品和液晶中。然而，获取这些高能中间体需要合成前体，这涉及苛刻的条件或多步合成。开发使用更简单的底物和更温和的条件获取芳烃的替代方法对于更简化的方法是必要的。在这里，我们描述了简单芳烃的两步正式脱氢，以在相对于传统反应性基团（例如卤化物）较远的位置生成芳烃。这种方法是通过区域选择性安装和弹出“鎓”离去基团实现的，我们证明了简单芳烃（20 个示例）和亲吻分子（8 个示例）的相容性。此外，通过直接比较，我们表明，与目前最先进的芳烃前体相比，我们的正式脱氢方法在生成芳烃方面更具官能团耐受性和效率。最后，我们证明芳炔中间体提供了不同于其他方法的区域选择性 C-H 胺化的机会。