Search results for "asymmetric hydrogenation"
showing 10 items of 15 documents
Unsymmetrical Iron P-NH-P' Catalysts for the Asymmetric Pressure Hydrogenation of Aryl Ketones.
2017
R.H.M. thanks NSERC Canada for a Discovery grant and the Canada Council for the Arts for a Killam Fellowship. This work was also made possible by the SCICOMP NMR facilities provided by the Canada Foundation for Innovation, project number 19119, and the Ontario Ministry of Research, Innovation and Science. The Deutscher Akademischer Austauschdienst (DAAD) is thanked for support for A.P. Calculations were performed using the facilities of SHARCNET and Scinet of Compute/Calcul Canada
Asymmetric Hydrogenation of Nonfunctionalized Olefins in Propylene Carbonate—Kinetic or Thermodynamic Control?
2011
Iridium-catalyzed hydrogenations of nonfunctionalized olefins in propylene carbonate as the solvent allow efficient catalysis with much higher enantioselectivities in comparison with dichloromethane which is usually employed for these reactions. Experimental and computational studies of the hydrogenation of 1-methylene-1,2,3,4-tetrahydronaphthalene have been performed to understand the limitation for this reaction.
Selective homogeneous hydrogenation of cycloocta-1,5, and cycloocta-1,3-diene to cyclooctene in the presence of (η4-cycloocta-1,5-diene)(η6-cycloocta…
1983
Cyclooctadiene isomers (1,3- and 1,5-COD) are selectively, homogenously hydrogenated to cyclooctene (C8H14) in tetrahydrofuran (THF) solution, under mild conditions of temperature (20 °C) and hydrogen pressure (1 atm), in the presence of catalytic amounts of (cycloocta-1,5-diene)(cycloocta-1,3,5,-triene)ruthenium(0), [Ru(η4-COD)(η6-C8H10)] (1). The rate of hydrogenation is higher when 1,3-COD is the substrate. Evidence for the isomerization 1,5-COD → 1,3-COD is reported. Similar studies carried out in several alcoholic solutions, although showing a decreased selectivity in the hydrogenation, confirm the isomerization 1,5-COD → 1,3-COD, and allow a discrimination between the isomerization an…
Supramolecular hydrogen-bonding tautomeric sulfonamido-phosphinamides: a perfect P-chirogenic memory
2011
P-chirogenic, supramolecular hydrogen-bonding C1-symmetrical sulfonamido–phosphinamides (METAMORPhos) have been successfully prepared. They were all found to possess a characteristic prototropic equilibrium between the PIII and the PV tautomers that is slow on the NMR spectroscopic timescale. Despite the dynamic and reversible protonation of the P centre, the P-chirogenic information was found to be retained in the tautomerization process, even in a protic solvent environment. Several strategies to access the corresponding enantiopure compounds were investigated, such as diastereoselective crystallization, or enantioselective synthesis. It was possible to resolve such a class of chiral liga…
Optically Active Titanium Complexes Containing Linked Amido‐cyclopentadienyl Ligands: Their Use as Asymmetric Hydrogenation Catalysts
1996
Optically active titanium complexes of the formula Ti(η5:η1−C5R4SiMe2NCHMePh)Cl2 (R = H, Me), containing the cyclopentadienyl ligand linked to a chiral 1-phenylethylamido moiety, were synthesized and characterized in both enantiomerically pure forms. A single-crystal X-ray structural analysis of (S)()Ti(η5:η1−C5H4SiMe2NCHMePh)Cl2 shows a conformation in which the phenyl group is turned away from the metal center. NOE measurements suggest that a related structure is retained in solution. Upon activation with n-butyllithium, these complexes show hydrogenation activity toward imines with slight enantioselectivity.
Asymmetric hydrogenation of ethyl pyruvate over aqueous dispersed Pt nanoparticles stabilized by a cinchonidine-functionalized β-cyclodextrin
2021
International audience; Cinchonidine-functionalized β-cyclodextrin was used as stabilizing agent for platinum nanoparticles dispersed in water, but also as chiral modifier for the asymmetric hydrogenation of ethyl pyruvate at 30 °C under 40 bar of hydrogen. This functionalized cyclodextrin allowed getting more stable, more catalytically active and also more enantioselective Pt nanoparticles compared to control catalytic systems. NMR and MALDI-MS analyses clearly showed the reduction of the vinyl group of the cinchonidine graft during the nanoparticles preparation. Under hydrogen pressure, the hydrogenation of the quinolinic moiety was also proven and can be responsible for the difficul…
Cyclodextrines confinantes : synthèse, propriétés complexantes et utilisation en catalyse asymétrique
2014
This manuscript is concerned with the design of novel catalytic systems derived from metallocyclodextrins. The first part describes new ways of functionalising the cyclodextrin primary face regioselectively for accessing inherently chiral P,P’ chelators. These heterodentate ligands gavequantitatively cis-chelate complexes with various d8 cations. Their rhodium(I) complexes were assessed in the asymmetric hydrogenation and hydroformylation of prochiral olefins. Thecoordination and catalytic properties of two phosphines derived from a- and b-cyclodextrin are also reported. With their phosphorus lone pair pointing toward the CD core, these confining ligands force the coordinated metal centre t…
Organic carbonates as alternative solvents for asymmetric hydrogenation
2009
Organic carbonates like propylene carbonate (PC) or butylene carbonate (BC) belong to the class of aprotic, highly dipolar solvents (AHD). Interestingly, their potential as solvents for asymmetric catalysis has been overlooked for a long time. The aim of this work is to evaluate organic carbonates and other organic solvents like THF, CH2Cl2, and acetonitrile as well as members of the AHD-family (DMF, DMSO, etc.) as media for homogeneous asymmetric hydrogenation. For this reason cationic Rh-complexes based on chiral phosphine ligands were tested in the hydrogenation of typical benchmark substrates. In several trials, significant advantages of organic carbonates were found. In contrast to DMS…
Modular P-Chirogenic Aminophosphane-Phosphinite Ligands for Rh-Catalyzed Asymmetric Hydrogenation: A New Model for Prediction of Enantioselectivity
2007
An original series of P-chirogenic aminophosphane-phosphinite (AMPP) ligands has been synthesized from (+)- or(–)-ephedrine in 23 to 61 % overall yields by a versatile three-step methodology. The AMPP ligands, bearing either one or two P-chirogenic centers, were used in the form of rhodium complexes for the catalyzed hydrogenation of α-acetamidocinnamate as a test reaction. Notably, even with AMPP ligands all derived from (+)-ephedrine, variation of the substituent on a P-center allowed the phenylalanine derivatives to be obtained in either (S) or (R) absolute configurations, with ee values ranging from 99 % (S) to 88 % (R). The asymmetric induction was analyzed with the aid of X-ray struct…
ChemInform Abstract: Stereoselective Synthesis of α-Arylalkylamines by Glycosylation-Induced Asymmetric Addition of Organometallic Compounds to Imine…
2009
Arylalkylamines are of interest as building blocks for the synthesis of biologically active compounds and as chiral ligands or chiral auxiliaries in stereoselective syntheses [1]. Their stereoselective synthesis has been achieved by enantioselective reduction of ketimines using chiral reagents [2], as for example Corey’s oxaborolidines [3], or proline-derived triacyloxyborohydrides [4]. Particularly efficient asymmetric syntheses of chiral arylalkylamines have been accomplished by Noyori et al. [5] through enantioselective catalysis of hydrogen transfer reactions using a chiral 1,2-diphenyl-ethylenediamine ruthenium catalyst. Enantioselective transferhydrogenationshave also been achieved us…