Department of Chemistry, College of Natural Science, Seoul National University, 1 Gwanak-ro, Seoul 08826, Republic of Korea.
Advanced Institutes of Convergence Technology, Suwon-si, Gyeonggi-do 16229 Republic of Korea.
J Am Chem Soc. 2022 May 25;144(20):9149-9160. doi: 10.1021/jacs.2c03213. Epub 2022 May 16.
Based on systematic electrochemical analysis, an integrated synthetic platform of C(sp)-based organoboron compounds was established for the introduction of heteroatoms. The electrochemically mediated bond-forming strategy was shown to be highly effective for the functionalization of sp-hybridized carbon atoms with significant steric hindrance. Moreover, virtually all the nonmetallic heteroatoms could be utilized as reaction partners using one unified protocol. The observed reactivity stems from the two consecutive single-electron oxidations of the substrate, which eventually generates an extremely reactive carbocation as the key intermediate. The detailed reaction profile could be elucidated through multifaceted electrochemical studies. Ultimately, a new dimension in the activation strategies for organoboron compounds was accomplished through the electrochemically driven reaction development.
基于系统电化学分析，建立了一个基于 C(sp) 的有机硼化合物的综合合成平台，用于引入杂原子。电介导键形成策略被证明对具有显著空间位阻的 sp 杂化碳原子的功能化非常有效。此外，几乎所有的非金属杂原子都可以使用一个统一的协议作为反应伙伴。观察到的反应性源于底物的两次连续单电子氧化，最终生成一个非常活泼的碳正离子作为关键中间体。通过多方面的电化学研究可以阐明详细的反应轮廓。最终，通过电驱动反应开发，实现了有机硼化合物的激活策略的新维度。
