Selective C(sp3)–H Arylation/Alkylation of Alkanes Enabled by Paired Electrocatalysis

We report a combination of electrocatalysis and photoredox catalysis to perform selective C(sp3)–H arylation/alkylation of alkanes for the first time, in which a binary catalytic system based on earth-abundant iron and nickel is applied. Reaction selectivity between two-component C(sp3)–H arylation and three-component C(sp3)–H alkylation is tuned by modulating the applied current and light source. Importantly, an ultra-low anodic potential (~0.23 V vs. Ag/AgCl) is applied in this protocol, thus enabling compatibility with a variety of functional groups (> 70 examples). The robustness of the method is further demonstrated on a preparative scale and applied to late-stage diversification of natural products and pharmaceutical derivatives.