While hypervalent halogens are versatile reagents enabling diverse reactions in organic synthesis, the utility of hypervalent chlorine compounds, particularly cyclic λ³-chloranes, remains underdeveloped despite their unique electronic properties and innate enhanced reactivity. Herein, we illustrate the elusive ligand coupling reaction of cyclic λ³-chloranes that suppresses the more facile competing reaction modality involving benzyne intermediates. The methodology can be performed in three-component as well as two-component fashions, offering direct access to a wide range of unsymmetrically substituted biaryl molecules in very high yields and excellent ortho-regioselectivity. The reactions were scalable, and the versatility was demonstrated by constructing different types of C–S and C–N bonds under mild conditions. The reaction outcomes were also compared with those of corresponding λ³-iodanes and λ³-bromanes, demonstrating the superiority of cyclic λ³-chloranes in ligand-coupling reactions under metal-free conditions.

中文翻译：

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使用环状二芳基 λ3-氯烷进行无金属位点选择性官能化：抑制配体偶联反应中的苯炔形成


虽然高价卤素是能够在有机合成中实现多种反应的多功能试剂，但高价氯化合物，特别是环状 λ ³ -氯烷，尽管具有独特的电子特性和固有的增强反应性，但其应用仍然不充分。在此，我们说明了环状 λ ³ -氯烷的难以捉摸的配体偶联反应，该反应抑制了涉及苯炔中间体的更容易的竞争反应方式。该方法可以以三组分和双组分的方式进行，以非常高的产率和优异的邻位选择性直接获得各种不对称取代的联芳基分子。该反应具有可扩展性，并且通过在温和条件下构建不同类型的 C-S 和 C-N 键证明了其多功能性。反应结果还与相应的λ ³ -碘烷和λ ³ -溴烷的反应结果进行了比较，证明了环状λ ³ -氯烷在无金属条件下配体偶联反应中的优越性。