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Selective Electrocatalytic Semihydrogenation of Alkynes by Water on a Pd–P Nanoparticle Network Cathode
Selective Transfer Semihydrogenation of Alkynes with H2O (D2O) as the H (D) Source over a Pd–P Cathode.
Angew. Chem. Int. Ed. 2020;
Key wordselectrocatalysis - semihydrogenation - alkynes - alkenes - palladium–phosphorus alloy - deuteration
A Pd–P alloy nanoparticle network (Pd–P NN), prepared according to Equation 1, promoted the selective electrocatalytic semihydrogenation of alkynes with H2O in aqueous 1,4-dioxane with 1.0 M KOH as an electrolyte to afford the corresponding alkenes in up to 95% yield and 99% selectivity. When the reaction was performed in 1,4-dioxane–D2O, the corresponding di- and trideuterated alkenes were obtained with 99% deuterium incorporation (Eq. 2). Monodeuterated alkenes were obtained by treatment of the alkynes with 0.5 M K2CO3 in 1,4-dioxane–D2O, followed by the electrocatalytic semihydrogenation in aqueous 1,4-dioxane containing a phosphate buffer (Eq. 3).
The Pd–P NN was characterized by means of SEM, TEM, EDX, XRD, XPS analyses. In the electrocatalytic semihydrogenation of 4-ethynylaniline, the catalyst was reused five times without significant loss of activity. The electrocatalytic semideuteration of 4-ethynylanisole was conducted on a gram scale to give 1.0 g of 1-(ethenyl-d 3)-4-methoxybenzene in 90% yield with 99% selectivity and 99% deuterium incorporation.
20 January 2021 (online)
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