Electrocatalytic Hydrogenation of Olefins

Electrochemical synthesis offers a powerful and sustainable alternative to conventional chemical manufacturing techniques. The direct and selective electrohydrogenation of olefins has enormous potential applicability; however, this reactivity has not been sufficiently demonstrated. Herein, we show that an efficient Pt‐based electrocatalyst from commercially available PtCl2 can promote such transformations. This approach enables olefins to be electrohydrogenated (often below −3.0 V vs. Ag/AgCl) at high current density (JGeo up to 133 mA/cm2) using protons and electrons as the hydrogen source. This reaction exhibits broad functional group compatibility, requires low catalyst loading, and affords a diverse series of valuable molecules (more than 70 examples) with high chemoselectivity. In addition, highly regioselective electrocatalytic hydrogenation of olefins (r.r. > 19:1) is demonstrated using PtCl2 and 2,2'‐bipyridine.