Electrocatalytic Hydrogenation of Olefins

Keywords

anodic oxidation - cathodic reduction - remote amino alcohols - copper-mediated reduction - cyclic amines

Significance

Highly chemoselective hydrogenation of olefins was achieved under electrochemical redox conditions in the presence of a platinum catalyst and a Brønsted acid, where protons and electrons served as the hydrogen source. More than 60 olefins bearing a wide variety of functional groups underwent the hydrogenation to give the corresponding alkanes. As a typical example, the hydrogenation of citronellyl benzoate (1) was carried out using Mg( + )/Fe(–) electrodes in an undivided cell with 3 mol% of PtCl₂ and 10 equivalents of valeric acid to afford a quantitative yield of dihydrocitronellyl benzoate (2).

 

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Comment

Terminal, cyclic, and trisubstituted alkenes were successfully hydrogenated to give the corresponding alkanes (e. g., 2, 3, 4, 6 and 7) in high yields. Strained ring systems, including a cyclopropane (10c), a cyclobutene (10 d), and an oxetane (8), were tolerated under the hydrogenation conditions. Boronic esters, aryl halides, and heteroarenes, which are potentially reactive with transition-metal catalysts, remained intact under the electrocatalytic conditions, demonstrating the high chemoselectivity of this hydrogenation (see products 5, 6, 7, 10a and 10b).

 

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Publication History

Article published online:
27 August 2025