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Selective Hydrogenations and Dechlorinations in Water Mediated by Anionic Surfactant-Stabilized Pd Nanoparticles

La Sorella, Giorgio, Sperni, Laura, Canton, Patrizia, Coletti, Lisa, Fabris, Fabrizio, Strukul, Giorgio, Scarso, Alessandro
Journal of organic chemistry 2018 v.83 no.14 pp. 7438-7446
Bronsted acids, aldehydes, alkenes, alkynes, anionic surfactants, aqueous solutions, catalysts, chemical structure, dechlorination, hydrogen, hydrogenation, ketones, mixing, nanoparticles, organic chemistry, polyethylene glycol, sodium dodecyl sulfonate, sodium dodecylbenzenesulfonate
We report a facile, inexpensive, and green method for the preparation of Pd nanoparticles in aqueous medium stabilized by anionic sulfonated surfactants sodium 1-dodecanesulfonate 1a, sodium dodecylbenzenesulfonate 1b, dioctyl sulfosuccinate sodium salt 1c, and poly(ethylene glycol) 4-nonylphenyl-3-sulfopropyl ether potassium salt 1d simply obtained by stirring aqueous solutions of Pd(OAc)₂ with the commercial anionic surfactants further treated under hydrogen atmosphere for variable amounts of time. The aqueous Pd nanoparticle solutions were tested in the selective hydrogenation reactions of aryl-alcohols, -aldehydes, and -ketones, leading to complete conversion to the deoxygenated products even in the absence of strong Brønsted acids in the reduction of aromatic aldehydes and ketones, in the controlled semihydrogenation of alkynes leading to alkenes, and in the efficient hydrodechlorination of aromatic substrates. In all cases, the micellar media were crucial for stabilizing the metal nanoparticles, dissolving substrates, steering product selectivity, and enabling recycling. What is interesting is also that a benchmark catalyst like Pd/C can often be surpassed in activity and/or selectivity in the reactions tested by simply switching to the appropriate commercially available surfactant, thereby providing an easy to use, flexible, and practical catalytic system capable of efficiently addressing a variety of synthetically significant hydrogenation reactions.