A fundamental property of cross-coupling reactions is regiospecificity, meaning that the site of bond formation is determined by the leaving group’s location on the electrophile. Typically, achieving a different substitution pattern requires the synthesis of a new, corresponding starting-material isomer. As an alternative, we proposed the development of cross-coupling variants that would afford access to multiple structural isomers from the same coupling partners. Here, we first demonstrate that a bulky palladium catalyst can facilitate the efficient, reversible transposition of aryl halides by temporarily forming metal aryne species. Despite the nearly thermoneutral equilibrium governing this process, combining it with the gradual addition of a suitable nucleophile results in dynamic kinetic resolution of the isomeric intermediates and high yields of unconventional product isomers. The method accommodates a range of oxygen- and nitrogen-centered nucleophiles and tolerates numerous common functional groups. A Curtin–Hammett kinetic scheme is supported by computational and experimental data, providing a general mechanistic framework for extending this migratory cross-coupling concept.

中文翻译：

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迁移芳基交叉偶联


交叉偶联反应的一个基本特性是区域特异性，这意味着键形成的位点由离去基团在亲电试剂上的位置决定。通常，实现不同的取代模式需要合成新的、相应的起始材料异构体。作为替代方案，我们建议开发交叉偶联变体，以便能够从相同的偶联伴侣获得多种结构异构体。在这里，我们首先证明了笨重的钯催化剂可以通过暂时形成金属芳烃物种来促进芳基卤化物的高效、可逆转座。尽管该过程处于近乎热中性的平衡状态，但将其与逐渐添加合适的亲核试剂相结合，可实现异构体中间体的动态动力学分离和非常规产物异构体的高产率。该方法适用于一系列以氧和氮为中心的亲核试剂，并耐受许多常见的官能团。科廷-哈米特动力学方案得到了计算和实验数据的支持，为扩展这种迁移交叉耦合概念提供了一个通用的机械框架。