Polyethylene glycol (PEG) was found to be an inexpensive, non‐toxic and recyclable reaction medium for ruthenium‐ and rhodium‐catalyzed asymmetric hydrogenation of 2‐arylacrylic acids (Ru‐catalyzed CC bond reduction), enamides (Rh‐catalyzed CC bond reduction), β‐keto esters and simple aromatic ketones (Ru‐catalyzed CO bond reduction). In all cases, high catalytic activities and enantioselectivities have been achieved, which are comparable to those obtained in conventional organic solvent systems. The Ru and Rh catalysts prepared with commercially available chiral diphosphine ligands could be readily recycled by simple extraction, as in the case of ionic liquids, and reused up to nine times without obvious loss of catalytic activity and enantioselectivity. The reduced products were obtained from the extracts in high isolated yields. These results indicate that PEGs as new reaction media are attractive alternatives to room temperature ionic liquids. 相似文献
Supported Ionic Liquid Catalysts (SILCA) designed by immobilization of catalytic species residing in an ionic liquid layer, which in turn was immobilized on a solid support, were applied on the selective hydrogenation of citral in a batch reactor and in a continuous reactor. Different ionic liquids with and without addition of acid modificators were studied in terms of the catalyst activity and product selectivity. Consequently, mechanistic kinetic models describing the differences in the activity and selectivity of the catalysts consisting different ionic liquids, were developed. 相似文献
A sulfonated chiral diamine ligand anion-based functionalized ionic liquid has been synthesized. Then the new ionic liquid-regulating ruthenium complexes were prepared successfully and employed as efficient catalysts for the asymmetric transfer hydrogenation of various ketones. The catalysts were highly efficient for the hydrogenation of a wide range of substrates bearing different functional groups and could be separated easily from the reaction mixture by thermoregulated phase separation, which can be efficiently recycled five times without significant changes in catalytic activity and enantioselectivity. 相似文献
The H2 reduction of RuO2 hydrate “dissolved” in 1-n-butyl-3-methylimidazolium ionic liquids with different counterions, hexafluorophosphate (BMI ? PF6), tetrafluoroborate (BMI ? BF4) and trifluoromethane sulfonate (BMI ? SO3CF3), is a simple and reproducible method for the preparation of ruthenium nanoparticles of 2.0–2.5?nm diameter size and with a narrow size distribution. The Ru nanoparticles were characterized by TEM and XRD. The isolated Ru nanoparticles are reoxidized in air, whereas they are less prone to oxidation when imbibed in the ionic liquids. These nanoparticles are active catalysts for the solventless or liquid–liquid biphasic hydrogenation of olefins under mild reaction conditions (4 atm, 75°C). The catalytic system composed of nanoparticles dispersed in BMI ? PF6 ionic liquid is very stable and can be reused several times without any significant loss in the catalytic activity. Total turnover numbers greater than 110 000 (based on total Ru) or 320 000 (corrected for exposed Ru atoms) were attained within 80?h for the hydrogenation of 1-hexene. 相似文献
Asymmetric hydrogenation reactions of quinolines and 3,4‐dihydroisoquinolines using the chiral cationic ruthenium complex Ru(TsDPEN) [TsDPEN=N‐(p‐toluenesulfonyl)‐1,2‐diphenylethylenediamine] as catalyst in neat imidazolium ionic liquids have been investigated. The catalytic performance was influenced by the anion of the ionic liquids for both substrate classes. A range of 2‐alkyl‐substituted 1,2,3,4‐tetrahydroquinolines and 1‐alkyl‐substituted 1,2,3,4‐tetrahydroisoquinolines was obtained in high yields with up to >99% ee. Interestingly, the hydrogenation of quinoline derivatives bearing a carbonyl group was selective for the CN (quinoline) over the CO (ketone) bonds, while such a unique chemoselectivity was not observed in methanol. Furthermore, the ruthenium catalysts could be easily recycled at least 5 times in the asymmetric hydrogenation of 3,4‐dihydroisoquinoline by solvent extraction. To further facilitate the recovery of catalyst and reduce the use of organic solvent, a thin film of ionic liquid containing Ru(TsDPEN) was supported on silica gels. This supported ionic liquid‐phase catalyst was effective in the asymmetric hydrogenation of quinoline, and could be recycled at least 6 times by simple filtration.
The heterogeneous sulfimidation of various sulfides by microencapsulated copper(II) acetylacetonate, [MC‐Cu(acac)2], and Cu(acac)2 immobilized in ionic liquids using [N‐(p‐tolylsulfonyl)imino]phenyliodinane (PhINTs) as nitrene donor has been developed to afford the corresponding sulfimides in good to excellent yields. In the presence of a chiral bis(oxazoline) as ligand, asymmetric induction occurs to afford the chiral sulfimides (up to 50% ee). The ionic liquid containing the immobilized bis(oxazoline)‐copper catalyst can be reused for several cycles with consistent activity and enantioselectivity. 相似文献