Synergistic Fe/Ni catalysis for electrochemical 1,1-difunctionalization of alkenes.

Alkene 1,1-difunctionalization holds significant importance in organic synthesis due to its ability to effectively enhance the complexity and functionality of molecular frameworks. Herein, we report an electrochemical strategy for 1,1-difunctionalization of halogenated aromatics with unactivated alkenes using synergistic Fe/Ni catalysis. This system integrates redox activity of nickel with Lewis acid functionality of iron: the nickel catalyst governs aryl halide oxidative addition and alkene migration, while iron species activates catalytic sites, stabilizes radical acceptors, and precisely regulates electrochemical reduction sequences/selectivities. The reaction system is applicable to a wide range of substrates, including electron-rich and electron-deficient aryl halides, polycyclic compounds, and bioactive natural products (100 examples). Gram-scale synthesis maintains 63% yield, supporting industrial viability. Mechanistic studies elucidate the unique cooperativity of this iron-nickel bimetallic system, providing a theoretical framework for the design of diverse difunctionalization reactions.