Mediator-Enabled Co-Catalyzed Z‑Selective Semihydrogenation via Hydride-Free Multisite Proton-Coupled Electron...

Redox mediators continue to emerge as powerful tools for driving electrochemical reactions, preventing electrode surface fouling and/or facilitating redox processes at milder operating potentials than direct electrolysis requires. In this study, we demonstrate a tandem electrocatalytic approach using a Cp₂Co redox mediator and (dppe)-CoCl₂ precatalyst to selectively hydrogenate a variety of alkynes to cis-alkenes. Controlled potential electrolysis (CPE) at the potential of the mediator (E _app = -1.45 V vs Fc^+/0) successfully generates a variety of terminal and internal alkenes in moderate to good yields. Notably, substrates with tethered Lewis bases further drive selectivity almost exclusively for the Z isomer. Mechanistic investigation of the tandem catalytic reaction via CV and DFT point toward a multisite proton-coupled electron transfer (MS-PCET) step involving a hydride-free pathway where Cp₂Co facilitates the reduction of alkyne- and acid-bound (dppe)-Co-(I)/(0). This developed methodology can be applied toward the synthesis of cis-stilbenoid natural products, as demonstrated with combretastatin A-4. It is also amenable to more practical gram-scale setup and proceeds with up to 99% Faradaic efficiency.