Synfacts 2021; 17(02): 0189
DOI: 10.1055/s-0040-1706656
Polymer-Supported Synthesis

Selective Electrocatalytic Semihydrogenation of Alkynes by Water on a Pd–P Nanoparticle Network Cathode

Contributor(s):
Yasuhiro Uozumi
,
Aya Tazawa
Wu Y, Liu C, Wang C, Lu S, Zhang B. * Tianjin University, P. R. of China
Selective Transfer Semihydrogenation of Alkynes with H2O (D2O) as the H (D) Source over a Pd–P Cathode.

Angew. Chem. Int. Ed. 2020;
59: 21170-21175
DOI: 10.1002/anie.202009757.
 

Significance

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).


#

Comment

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.


#
#

Publication History

Publication Date:
20 January 2021 (online)

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany