The development of a methodology for the preparation of arylboronic acids or arylboronates is of significant interest to organic chemists. Classical synthetic methods to prepare these organoboron compounds are based on the reaction of Grignard or lithium reagents with trialkyl borates. In the past few decades, the transition‐ metal‐catalyzed borylation of aryl halides, or pseudohalides, and C–H bonds of hydrocarbons has been a powerful tool for the synthesis of arylboronates in modern organic synthesis. These transformations are generally considered to proceed via organometallic intermediates generated by oxidative addition or transmetalation processes from the boron reagent. Several reviews on this type of borylation catalyzed by transition metals have been published in the literature. Interestingly, there has been a novel recognition that the boron reagent can participate in free‐radical coupling via the homolytic cleavage of the boron‐boron bond in recent years. In this review, recent advances in this new area of boron chemistry are summarized and the reaction mechanisms are also discussed.

中文翻译：

---

通过自由基途径形成C-B键的最新进展

有机化学家对制备芳基硼酸或芳基硼酸酯的方法学的开发非常感兴趣。制备这些有机硼化合物的经典合成方法是基于格氏试剂或锂试剂与硼酸三烷基酯的反应。在过去的几十年中，过渡金属催化的芳基卤化物或假卤化物的硼化以及烃的CH键已成为现代有机合成中芳基硼酸酯合成的有力工具。这些转换通常被认为是通过以下方式进行的硼试剂通过氧化加成或过金属化过程生成的有机金属中间体。关于过渡金属催化的这种类型的硼化作用的一些评论已在文献中发表。有趣的是，近年来人们有了新的认识，即硼试剂可以通过硼-硼键的均质裂解来参与自由基偶联。在这篇综述中，总结了硼化学这一新领域的最新进展，并讨论了反应机理。