State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
Chem Rev. 2020 Aug 12;120(15):7348-7398. doi: 10.1021/acs.chemrev.9b00384. Epub 2020 Jun 29.
Organoborons have emerged as versatile building blocks in organic synthesis to achieve molecular diversity and as carboxylic acid bioisosteres with broad applicability in drug discovery. Traditionally, these compounds are prepared by the substitution of Grignard/lithium reagents with electrophilic boron species and Brown hydroboration. Recent developments have provided new routes for the efficient preparation of organoborons by applying reactions using chemical feedstocks with leaving groups. As compared to the previous methods that used organic halides (I, Br, and Cl), the direct borylation of less reactive C-Het and C-C bonds has become highly important to get efficiency and functional-group compatibility. This Review aims to provide a comprehensive overview of this topic, including (1) C-F bond borylation, (2) C-O bond borylation, (3) C-S bond borylation, (4) C-N bond borylation, and (5) C-C bond borylation. Considerable attention is given to the strategies and mechanisms involved. We expect that this Review will inspire chemists to discover more efficient transformations to expand this field.
有机硼化合物已成为有机合成中多功能的构建模块，可实现分子多样性，并可作为羧酸生物等排体，在药物发现中具有广泛的适用性。传统上，这些化合物是通过格氏试剂/锂试剂与亲电硼物种的取代反应和布朗硼氢化反应制备的。最近的发展为通过使用带有离去基团的化学原料进行反应提供了制备有机硼化合物的新途径。与以前使用有机卤化物（I、Br 和 Cl）的方法相比，直接对反应性较低的 C-Het 和 C-C 键进行硼化反应对于提高效率和官能团兼容性变得非常重要。本综述旨在全面概述这一主题，包括（1）C-F 键硼化反应，（2）C-O 键硼化反应，（3）C-S 键硼化反应，（4）C-N 键硼化反应，以及（5）C-C 键硼化反应。本综述还特别关注了所涉及的策略和机制。我们希望这篇综述能激发化学家们发现更多有效的转化方法来拓展这一领域。
