Electrocatalytic Hydrogenation of Olefins

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

Abstract Electrochemical synthesis offers a powerful and sustainable alternative to conventional chemical manufacturing techniques. The direct selective electrohydrogenation of olefins has enormous potential applicability; however, this reactivity not been sufficiently demonstrated. Herein, we show that an efficient Pt‐based electrocatalyst from commercially available PtCl 2 can promote such transformations. This approach enables be electrohydrogenated (often below −3.0 V vs. Ag/AgCl) at high current density ( J Geo up 133 mA cm −2 ) using protons electrons as the hydrogen source. reaction exhibits broad functional group compatibility, requires low catalyst loading, affords diverse series valuable molecules (more than 60 examples) with chemoselectivity. In addition, highly regioselective electrocatalytic hydrogenation (r.r. > 19:1) is demonstrated 2,2′‐bipyridine.

Language: Английский

Proton-Modulated Nickel Hydride Electrocatalysis for the Hydrogenation of Unsaturated Bonds and Olefin Isomerization

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 21, 2025

Transition-metal hydrides stand as indispensable intermediates in both energy conversion and organic synthesis. Their electrochemical generation represents a compelling sustainable approach, enabling precise control over the reactivity expanding scope of electrocatalytic hydrogenation isomerization. However, major challenge Ni-catalyzed is competing hydrogen evolution reaction (HER), which has led to various innovative strategies aimed at circumventing Ni-H formation. Here, we pursued an alternative approach by designing bifunctional ligand with pendant amine moiety promote This design enabled selective (semi)hydrogenation diverse range substrates, including terminal internal alkynes, alkenes, aldehydes, achieving unprecedented substrate scope. Remarkably, also demonstrated tunable positional selectivity for olefin isomerization employing different types proton sources. Our method exhibits excellent functional group tolerance, streamlining access pharmaceuticals their derivatives. Computational studies revealed crucial, noninnocent role source modulating metal hydride selectivity, either through bonding, direct protonation amine, or facilitation protodemetalation.

Language: Английский