Selective palladium nanoparticles-catalyzed hydrogenolysis of industrially targeted epoxides in water
نویسندگان
چکیده
Palladium nanoparticles, with core sizes of ca. 2.5 nm, were easily synthesized by chemical reduction Na2PdCl4 in the presence hydroxyethylammonium salts and proved to be efficient for selective hydrogenolysis various aromatic, alkylphenyl, aliphatic epoxides water as green solvent. Capping agents metal species screened define most suitable micellar nanoreactors on two target substrates industrial interest, epoxystyrene 7,8-epoxy-2-methoxy-2,6-dimethyloctane. In our conditions, pH-dependent, producing either diol under acidic or sweet-smelling 2-phenylethanol a base. Promisingly, 7,8-epoxy-2-methoxy-2,6-dimethyloctane was completely selectively hydrogenated into Florsantol®, sandalwood odorant at multigram scale (40 g up 175g). A general mechanism palladium nanoparticles-catalyzed terminal proposed according steric electronic properties finely corroborated deuterium labelling experiments.
منابع مشابه
Selective, nickel-catalyzed hydrogenolysis of aryl ethers.
Selective hydrogenolysis of the aromatic carbon-oxygen (C-O) bonds in aryl ethers is an unsolved synthetic problem important for the generation of fuels and chemical feedstocks from biomass and for the liquefaction of coal. Currently, the hydrogenolysis of aromatic C-O bonds requires heterogeneous catalysts that operate at high temperature and pressure and lead to a mixture of products from com...
متن کاملFormal palladium-catalyzed asymmetric hydrogenolysis of racemic N-sulfonyloxaziridines.
Highly enantioselective palladium-catalyzed formal hydrogenolysis of racemic N-sulfonyloxaziridines has been realized, providing a novel access to sultams with up to 99% ee. Preliminary mechanistic insights revealed that the reaction proceeded through a N-O bond cleavage, dehydration, and the sequential asymmetric hydrogenation.
متن کاملPalladium-catalyzed selective fluorination of o-carboranes.
A Pd(II)-catalyzed direct selective fluorination reaction of carboranes using a F(+) reagent has been developed, leading to a series of polyfluorocarboranes in high isolated yields. The mechanism involving electrophilic B-H activation, oxidation of Pd(II) by F(+) species, and reductive elimination is proposed.
متن کاملEfficient Palladium-Catalyzed C O Hydrogenolysis of Benzylic Alcohols and Aromatic Ketones with Polymethylhydrosiloxane
A simple method has been developed for the reductive deoxygenation of aromatic ketones and benzylic alcohols in the presence of polymethylhydrosiloxane (PMHS). The reductive deoxygenation of aromatic ketones and benzylic alcohols, including secondary alcohols, to the corresponding methylene hydrocarbons has been achieved in good to excellent yields using palladium chloride (PdCl2) as catalyst a...
متن کاملPalladium-catalyzed asymmetric hydrogenolysis of N-sulfonyl aminoalcohols via achiral enesulfonamide intermediates.
Hydrogenolysis is an important synthetic method in organic chemistry, and has been widely applied in industrial processes, natural product synthesis, and the removal of waste materials. In practice, most hydrogenolysis reactions have been used for the synthesis of racemic or achiral compounds. Very few studies on asymmetric homogeneous hydrogenolysis have been reported. The first example, repor...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
ژورنال
عنوان ژورنال: Journal of Catalysis
سال: 2021
ISSN: ['0021-9517', '1090-2694']
DOI: https://doi.org/10.1016/j.jcat.2021.02.027