Arynes hold significance for the efficient fusion of (hetero) arenes with diverse substrates, advancing the construction of complex molecular frameworks. Employing multiple equivalents of arynes is particularly effective in the rapid formation of polycyclic cores found in optoelectronic materials and bioactive compounds. However, the inherent reactivity of arynes often leads to side reactions, yielding unanticipated products and underlining the importance of a detailed investigation into the use of multiple arynes to fine-tune their reactivity. This review centers on methodologies and syntheses in organic reactions involving multiple arynes, categorizing based on mechanisms like cycloadditions, σ-bond insertions, nucleophilic additions, and ene reactions, and discusses aryne polymerization. The categorization based on these mechanisms includes two primary approaches: the first entails multiple aryne engagement within a single step while the second approach involves using a single equivalent of aryne sequentially across multiple steps, with both requiring strict reactivity control to ensure precise aryne participation in each respective step. Additionally, the review provides an in-depth analysis of the selection of aryne precursors, organized chronologically and by activation strategy, offering a comprehensive background that supports the main theme of multiple aryne utilization. The expectation remains that this comprehensive review will be invaluable in designing advanced syntheses engaging multiple arynes.

中文翻译：

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Aryne 化学：掺入多个 Aryne 的生成方法和反应


芳烃对于（异）芳烃与不同底物的高效融合具有重要意义，可推进复杂分子框架的构建。使用多个当量的芳烷在快速形成光电材料和生物活性化合物中的多环核方面特别有效。然而，芳烃的固有反应性通常会导致副反应，产生意想不到的产物，并强调了对使用多个芳烃进行详细研究以微调其反应性的重要性。本文重点介绍涉及多个芳烷的有机反应的方法和合成，根据环加成反应、σ键插入、亲核加成反应和烯反应等机制进行分类，并讨论了芳烃聚合。基于这些机制的分类包括两种主要方法：第一种需要在单个步骤中实现多个 aryne 结合，而第二种方法涉及在多个步骤中依次使用单个 aryne 当量，这两种方法都需要严格的反应性控制，以确保 aryne 精确地参与每个相应的步骤。此外，该综述还对芳烃前驱体的选择进行了深入分析，按时间顺序和活化策略组织，提供了支持多种芳烃利用主题的全面背景。人们仍然期望这种全面的综述在设计涉及多个芳烃的高级合成方面具有不可估量的价值。