The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, 430072, P. R. China.
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, P. R. China.
Angew Chem Int Ed Engl. 2023 Mar 27;62(14):e202218179. doi: 10.1002/anie.202218179. Epub 2023 Feb 20.
This report describes the unprecedented electrooxidation of a solvent (e.g., DMF)-ligated B cat complex, whereby a solvent-stabilized boryl radical is formed via quasi-homolytic cleavage of the B-B bond in a DMF-ligated B cat radical cation. Cyclic voltammetry and density functional theory provide evidence to support this novel B-B bond activation strategy. Furthermore, a strategy for the electrochemical gem-diborylation of gem-bromides via paired electrolysis is developed for the first time, affording a range of versatile gem-diborylalkanes, which are widely used in synthetic society. Notably, this reaction approach is scalable, transition-metal-free, and requires no external activator.
本报告描述了一种前所未有的溶剂（例如 DMF）配位 B 催化剂配合物的电氧化反应，其中通过 DMF 配位的 B 催化剂自由基阳离子中 B-B 键的准均裂形成了溶剂稳定的硼自由基。循环伏安法和密度泛函理论提供了证据支持这种新型 B-B 键活化策略。此外，首次开发了一种通过成对电解电化学进行偕二溴化物的Gem-二硼化的策略，得到了一系列广泛应用于合成领域的多功能偕二硼基烷烃。值得注意的是，这种反应方法具有可扩展性、无需使用过渡金属且无需外部活化剂。
