Electrooxidative Activation of B−B Bond in B2cat2: Access to gem‐Diborylalkanes via Paired Electrolysis

Abstract

AbstractThis report describes the unprecedented electrooxidation of a solvent (e.g., DMF)‐ligated B2cat2 complex, whereby a solvent‐stabilized boryl radical is formed via quasi‐homolytic cleavage of the B−B bond in a DMF‐ligated B2cat2 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.