Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required to enable their C(sp 3 )À H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating oxidative catalysis with reductive catalysis in one cell without interference, in which earth-abundant iron and nickel are employed as the anodic and cathodic catalysts, respectively. This approach lowers the previously high oxidation potential required for alkane activation, enabling electrochemical alkane functionalization at the ultra-low oxidation potential of � 0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

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 BÀ B bond in a DMF-ligated B 2 cat 2 radical cation. Cyclic voltammetry and density functional theory provide evidence to support this novel BÀ B bond activation strategy. Furthermore, a strategy for the electrochemical gemdiborylation 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.

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 BÀ B bond in a DMF-ligated B 2 cat 2 radical cation. Cyclic voltammetry and density functional theory provide evidence to support this novel BÀ B bond activation strategy. Furthermore, a strategy for the electrochemical gemdiborylation 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.

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required to enable their C(sp 3 )À H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating oxidative catalysis with reductive catalysis in one cell without interference, in which earth-abundant iron and nickel are employed as the anodic and cathodic catalysts, respectively. This approach lowers the previously high oxidation potential required for alkane activation, enabling electrochemical alkane functionalization at the ultra-low oxidation potential of � 0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required to enable their C(sp3)−H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating oxidative catalysis with reductive catalysis in one cell without interference, in which earth-abundant iron and nickel are employed as the anodic and cathodic catalysts, respectively. This approach lowers the previously high oxidation potential required for alkane activation, enabling electrochemical alkane functionalization at the ultra-low oxidation potential of ~0.25 V under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed via this electrochemical C(sp3)−H alkenylation using readily available alkenyl electrophiles.