Electrooxidative Activation of B−B Bond in B<sub>2</sub>cat<sub>2</sub>: Access to <i>gem</i>‐Diborylalkanes via Paired Electrolysis
Bingbing Wang, Xiangyu Zhang, Yangmin Cao, Long Zou, Xiaotian Qi, Qingquan Lu
Abstract
Abstract This report describes the unprecedented electrooxidation of a solvent (e.g., DMF)‐ligated B 2 cat 2 complex, whereby a solvent‐stabilized boryl radical is formed via quasi‐homolytic cleavage of the B−B bond in a DMF‐ligated B 2 cat 2 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.