发明名称 Catalyst composition for enantioselective hydrogenation of unsaturated compounds, e.g. olefins, comprises a transition metal component, a tropoisomeric or racemic chiral ligand and a chiral ionic liquid
摘要 #CMT# #/CMT# A catalyst composition (I) comprising (A) a transition metal component, (B) a ligand component and (C) a chiral diluent component, in which (B) contains at least one tropoisomeric or racemic chiral ligand and (C) contains at least one chiral ionic liquid. #CMT# : #/CMT# An independent claim is included for a method for the enantioselective catalytic hydrogenation of unsaturated compounds in which the catalyst (I) is formed in situ by mixing the components. #CMT#USE : #/CMT# For the enantioselective hydrogenation, hydroboration, hydrosilylation, hydrovinylation, isomerisation, hydrocyanation and/or hydroformylation of unsaturated compounds (claimed). Used especially for the hydrogenation of ketones, imines and/or olefins. #CMT#ADVANTAGE : #/CMT# An easily-handled catalyst composition enabling good/high enantioselectivity in the homogeneous catalytic enantioselective hydrogenation, hydroboration, hydrosilylation, hydrovinylation, isomerisation, hydrocyanation and/or hydroformylation of unsaturated compounds, plus recovery of the catalyst composition on the industrial scale. #CMT#INORGANIC CHEMISTRY : #/CMT# Preferred Component: Component (A) contains rhodium, iridium, ruthenium, palladium, nickel, cobalt, platinum, copper, iron, gold, zinc, titanium and/or zirconium. #CMT#ORGANIC CHEMISTRY : #/CMT# Preferred Components: Component (B) comprises phosphorus, nitrogen and/or sulfur compound(s), especially phosphanes, phosphates, phosphonites, phosphinites, phosphoramidites, phosphorotriamides, diphosphanes, phosphane-phosphoramides, phosphane-phosphites, diphosphites, diphosphinites, amines, pyridines, quinolines, oxazolines, phosphorus-nitrogen compounds, thioethers, sulfoximines, sulfoxides and/or phosphorus-sulfur compounds. Component (C) comprises (c1) chiral anion(s) and an achiral and/or chiral cation, or (c2) chiral cation(s) and an achiral and/or chiral anion. Preferred chiral anions contain a carboxylate and/or sulfonate group and optionally another functional group, especially an ester, amide, ether, alcohol, amino, carboxylic acid, phosphoric acid, phosphate ester, sulfonic acid, sulfonate ester and/or sulphonamide group. Suitable chiral cations contain an ammonium ion with centre(s) or element(s) of chirality and optionally another functional group, especially those listed above; preferred chiral cations are based on those of natural or non-natural alpha -, beta - or gamma -amino acids or their derivatives. (I) may also contain an achiral additive, preferably selected from organic solvents, water, bases, acids and ionic liquids, especially methanol, ethanol, isopropanol, 1-octanol, THF, acetone, dichloromethane, benzene, toluene, DMSO, DMF, tri- or di-ethylamine, di-isopropylethylamine, pyridine, N-methylpyrrolidine, imidazole, methylimidazole, pyrrolidine, pyrrole, aniline, quinoline, acetic acid, trifluoroacetic acid, or ionic liquids selected from the combination of cations EMIM, BMIM, BEIM, methylpyridinium, ethylpyridinium, trioctyl-methyl-ammonium, tributyl-methyl-ammonium and/or tetrabutyl-ammonium with the anions N(SO 2CF 3) 2, PhSO 3, CF 3COO, CF 3SO 3and/or N(CN) 2.Preferred Method: Catalytic hydrogenation of ketones, imines and/or olefins, carried out as a continuous process at -78 to 200 (preferably 0-60) [deg] C with a hydrogen partial pressure of 0.01-400 (preferably 1-100) bar, followed by extraction with compressed carbon dioxide and recycling of the catalyst composition (I). #CMT#EXAMPLE : #/CMT# A solution of 34.5 g L-proline in 300 ml methanol was treated at -10[deg] C with 78 ml thionyl chloride, stirred for 12 hours at room temperature (RT) and evaporated to dryness. The residue was dissolved in water and the solution was treated with an aqueous solution of 90 g lithium bis-(trifluoromethylsulfonyl)-amide, stirred for 30 minutes at RT and worked up by extraction with dichloromethane (DCM), washing with water and evaporation of solvent, to give 87.3 g (71%) L-proline methyl ester bis-(trifluoromethylsulfonyl)-amide (ionic liquid; IL6) (characterised by 1>H- and 13>C-NMR analysis. A solution of 0.013 mmol 2,2'-bis-diphenylphosphanyl-1,1'-binaphthyl (BINAP; ligand 5) in 0.8 ml IL6 was treated with a solution of 0.012 mmol 2,4-pentanedionyl-rhodium dicarbonyl in 2 ml DCM, followed after 10 minutes by 2.4 mmols (S)-2,3-bis-methoxycarbonyl-prop-1-ene (7b), and then hydrogenated at 40 bar (hydrogen) for 16 hours, although constant pressure was reached after less than 1 hour. GC analysis showed quantitative conversion to 1,2-bis-methoxycarbonylpropane, with an enantiomeric excess (ee) of 70% for the (S) enantiomer; if the (R) enantiomer of the substrate (7b) was used, the ee was 66% for the (R) form of the product.
申请公布号 DE102007040333(A1) 申请公布日期 2009.02.26
申请号 DE20071040333 申请日期 2007.08.24
申请人 RHEINISCH-WESTFAELISCHE TECHNISCHE HOCHSCHULE AACHEN 发明人 FRANCIO, GIANCARLO;KLANKERMAYER, JUERGEN;LEITNER, WALTER;SCHMITKAMP, MIKE;DIANJUN, CHEN
分类号 B01J31/16;B01J31/02;B01J31/18;B01J31/24 主分类号 B01J31/16
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