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[ CAS No. 24915-95-5 ]

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Chemical Structure| 24915-95-5
Chemical Structure| 24915-95-5
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CAS No. :24915-95-5 MDL No. :MFCD00075386
Formula : C6H12O3 Boiling Point : 175°C at 760 mmHg
Linear Structure Formula :- InChI Key :N/A
M.W :132.16 g/mol Pubchem ID :440030
Synonyms :

Safety of [ 24915-95-5 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P264-P271-P280-P302+P352-P304+P340+P312-P305+P351+P338-P312-P332+P313-P337+P313-P403+P233-P405-P501 UN#:N/A
Hazard Statements:H302+H312-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 24915-95-5 ]

  • Downstream synthetic route of [ 24915-95-5 ]

[ 24915-95-5 ] Synthesis Path-Downstream   1~15

  • 1
  • [ 64-17-5 ]
  • [ 625-72-9 ]
  • [ 24915-95-5 ]
  • 2
  • [ 110-87-2 ]
  • [ 24915-95-5 ]
  • ethyl (R)-β-tetrahydropyranyloxybutyrate [ No CAS ]
YieldReaction ConditionsOperation in experiment
92.5% With pyridinium p-toluenesulfonate In dichloromethane for 3h; Ambient temperature;
  • 3
  • [ 67-56-1 ]
  • [ 24915-95-5 ]
  • [ 3976-69-0 ]
YieldReaction ConditionsOperation in experiment
98% at 64℃; for 10h;
82% autoclave, 1.) 160 deg C, 17 bar, 2 h; 2.) 115 deg C, 3.5 bar, 27 h;
  • 4
  • [ 5405-41-4 ]
  • [ 24915-95-5 ]
YieldReaction ConditionsOperation in experiment
99% With alcohol dehydrogenase from Thermoanaerobium brockii; NADH-specific (R)-selective-ADH; YcnD-oxidoreductase at 30℃; for 24h; aq. buffer; Resolution of racemate; Enzymatic reaction; optical yield given as %ee; enantiospecific reaction;
Multistep reaction.;
  • 5
  • [ 5405-41-4 ]
  • [ 24915-95-5 ]
  • [ 56816-01-4 ]
YieldReaction ConditionsOperation in experiment
Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With pentyl cage-coated capillary column Resolution of racemate;
With homochiral metal-organic cage [Zn3(deprotonated [3+3] macrocyclic Schiff base of trans-1,2-diaminocyclohexane and 4-tert-butyl-2,6-diformylphenol)2] coated capillary column In dichloromethane at 118℃; Resolution of racemate; enantioselective reaction;
  • 6
  • [ 24915-95-5 ]
  • [ 111-83-1 ]
  • (R)-2-((R)-1-Hydroxy-ethyl)-decanoic acid ethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
66% With lithium diisopropyl amide In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide
  • 7
  • [ 24915-95-5 ]
  • [ 112-29-8 ]
  • (R)-2-((R)-1-Hydroxy-ethyl)-dodecanoic acid ethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
66% With lithium diisopropyl amide In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide
  • 8
  • [ 24915-95-5 ]
  • [ 870-50-8 ]
  • [ 122886-50-4 ]
  • [ 122886-49-1 ]
YieldReaction ConditionsOperation in experiment
With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 0.05h; Yield given. Yields of byproduct given;
Stage #1: Ethyl (R)-3-hydroxybutanoate With lithium diisopropyl amide In tetrahydrofuran at -60 - 20℃; Inert atmosphere; Stage #2: di-tert-butyl-diazodicarboxylate In tetrahydrofuran at -78℃; Stage #3: With acetic acid In tetrahydrofuran at -78℃; for 0.25h; 10.A Example 10: Part A:A solution of lithium diisopropylamide (LDA, 1.8M, 14.3 mL, 25.7 mmoS) in THF (30 rnL) was cooled to -60 0C under an argon atmosphere. (R)-Ethyl 3-hydroxybutanoate (800 μL, 6.11 mmo.) was diluted with THF (5 mL) and the resulting solution transferred to the stirring lithium diisopropylamide solution. The reaction mixture was warmed to - 20 0C over 30 minutes. The resuiting dianion was cooled to -78 0C and a solution of di-terf-butylazodicarboxylate (3.52 g, 15.3 mmol) in THF (7 mL) slowly added. The reaction mixture was stirred at -78 0C for a further 10 minutes before quenching with AcOH (2.1 mL, 36.7 mmol). The reaction mixture was stirred at -780C for an additional 15 minutes, warmed to room temperature, diluted with water and extracted with EtOAc, Drying over magnesium sulfate, concentration and purification by flash column chromatography, gradient elution (0 to 100 %) hexane / ethyl acetate, afforded the separation of both diastereomers of compound 55 as a colorless oil (2.0 g, 91 % yield). Diastereomer 1 : HPLC-MS tR - 1.94 min (UV254 nm); mass calculated for formula Ci6H30N2O7362.2, observed LCMS m/z 385.2 (M+Na). Diastereomer 2: HPLC-MS tR = 2.10 min (UV254 nm); mass calculated for formula Ci6H30N2O7362.2, observed LCMS m/z 385.2 (M+Na).
  • 9
  • [ 24915-95-5 ]
  • [ 89238-99-3 ]
  • [ 120400-77-3 ]
YieldReaction ConditionsOperation in experiment
86% With (1S)-10-camphorsulfonic acid In dichloromethane for 25h; Ambient temperature;
  • 10
  • [ 24915-95-5 ]
  • [ 6290-03-5 ]
YieldReaction ConditionsOperation in experiment
81% General procedure: This method was adapted from the literature.14 To a suspension of LiAlH4 (7.6 mmol, 1 equiv) in dry diethyl ether (6 mL) was added a solution of beta-hydroxyester (7.6 mmol, 1 equiv) in dry diethyl ether (5 mL) at 0 C. The mixture was stirred for 3 h at room temperature and then quenched with distilled water (1 mL). After 10 mn, a 30% NaOH solution (1.5 mL) was added followed by 1 mL of distilled water. The reaction mixture was passed through a Celite pad. The filtrate was dried over MgSO4, concentrated under vacuum and purified by column chromatography if necessary (silica gel, cyclohexane/ethyl acetate 20/80) to afford the desired diol.
A heavy duty stainless steel stock pot is charged with 12 L water and a portion of (3.49L)ethyl (R) 3-hydroxybutyrate. Both water and ester were previously chilled to 4 C for at least24 h. The stock pot is surrounded by ice, gassed with nitrogen and stirred. After about 1 h,1Kg sodium borohydride is added in small aliquots to order to minimize temperature gain. Borohydride addition takes about 1 h and the temperature should be kept below 20 C during the NaBH4 addition. About 5 h after borohydride addition the reaction is quenched by slowly adding 745 ml concentrated sulfuric acid. The mixture is allowed to stand, with stirring overnight and the temperature rise to room temperature. The mixture is filtered, thefiltrate heated to 90C and neutralized* by adding calcium hydroxide with stirring. . After 2 hours mixture is cooled and filtered and the filtrate ionic strength reduced using ion exchange resins after which the solution is placed on a Buchi Rotovap and the bulk of the water removed. This leaves a viscous liquid assaying to > 10 M (R) 1,3-butanediol and containing 5-10% water. Remaining water is removed by nitrogen purge or distillation. Thepurity is checked by enzymatic assay, GO-MS and NMR.
  • 11
  • [ 24915-95-5 ]
  • [ 625-72-9 ]
YieldReaction ConditionsOperation in experiment
85% With sodium hydroxide; In water; at 10℃; for 6h; In a 500ml three-vial bottle,Ethyl (R)-3-hydroxybutyrate (87.5 g) obtained in Example 2 was added and 300 ml of water was added.Control temperature is less than 10 C,Slowly add sodium hydroxide solids (26.5 g) in batches over 3 hours.Control temperature is not higher than 10 C,After the addition, continue to react for 3 hours.The reaction solution was directly passed through 732 cation exchange resin,Get (R)-3-hydroxybutyric acid in water,Concentrate to near anhydrouscrystallization,Centrifugation,Obtained 58.6g of white solid R-3-hydroxybutyric acid,Yield 85.0%,The ee value is 92%.
With sodium hydroxide; In ethanol; water; In a liquid mixture comprising 15 ml of water, 15 ml of ethanol and sodium hydroxide was dissolved 4.0 g of ethyl (R)-beta-hydroxybutanoate, and the solution was heated and refluxed for 3 hours and then cooled. Then, the solution was subjected to an ion exchange treatment with an ion exchange resin (Amberlite R120B supplied by Rohm & Haas). The solvent was removed by distillation under a reduced pressure to obtain 3.6 g of (R)-beta-hydroxybutanoic acid.
  • 12
  • [ 24915-95-5 ]
  • [ 117706-97-5 ]
YieldReaction ConditionsOperation in experiment
With diisobutylaluminium hydride In dichloromethane; toluene at -90℃;
With diisobutylaluminium hydride In dichloromethane; toluene at -76℃; for 2h;
  • 13
  • [ 141-97-9 ]
  • [ 6168-83-8 ]
  • [ 625-72-9 ]
  • [ 24915-95-5 ]
  • [ 56816-01-4 ]
  • 14
  • [ 141-97-9 ]
  • [ 24915-95-5 ]
YieldReaction ConditionsOperation in experiment
100% With (S)-4,12-bis(diphenylphosphino)-<2.2>paracyclophane-Ru(II)bis(trifluoroacetate); hydrogen; tetra-(n-butyl)ammonium iodide In methanol; water at -5℃; for 18h;
100% With hydrogen In ethanol; dichloromethane at 70℃; for 1h;
100% With [(+)-N,N'-Me2-3,3'-(Ph2P)2-1,1'-biindole]RuCl2; hydrogen In methanol; water at 45℃; for 0.5h;
100% With dichloro-R-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl ruthenium; hydrogen In ethanol
99% With hydrogen In methanol at 50℃; for 24h; optical yield given as %ee; enantioselective reaction;
99% With hydrogen In methanol at 50℃; for 24h; Autoclave; enantioselective reaction;
98% With hydrogen In ethanol at 55℃; for 24h;
98.5% With dichloro(benzene)ruthenium(II) dimer In methanol at 80℃; for 20h; Inert atmosphere; Autoclave; 2 Example 2: Synthesis of ethyl (R)-3-hydroxybutyrate Under a nitrogen atmosphere,In a 3-liter autoclave,The dichlorophenyl ruthenium (II) dimer [RuCl2 (benzene) 2](80mg, 160umol),(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-dibenzofuranyl-8,8'-disulfonic acid dipotassium salt ligand (340umol)Ethyl 3-oxobutanoate (86 ml, 680 mmol) was dissolved in methanol (600 ml).Degassing under reduced pressure,After purging the autoclave with nitrogen,The hydrogenation reaction was carried out at 80° C. and a hydrogen pressure of 10 bar for 20 hours.Cool to room temperatureConcentrate to near dryness,A mixture of catalyst and ethyl (R)-3-hydroxybutyrate is obtained;Slowly warming up to 85°CObtained 88.4 g of colorless (R)-3-hydroxybutyrate,Yield 98.5%,The ee value is 94.5%.Recycling catalystCan be reused after regeneration.The concentrated methanol recovered can be used directly.
97.4% With Acetobacter sp. CCTCC M209061 anti-Prelog carbonyl reductase mut-I147V/G152L mutant; isopropyl alcohol; NADH In aq. phosphate buffer at 35℃; for 4h; Enzymatic reaction; enantioselective reaction;
95% With hydrogen In methanol at 70℃; for 2h;
95% With D-glucose; broth E. coli HB101; pNTS1G; NADP In various solvent(s) at 30℃; for 20h; Enzymatic reaction;
95% With hydrogenchloride; [RuCl2-((R)-binap)]*NEt3; hydrogen In methanol; water at 50℃; for 16h; optical yield given as %ee; enantioselective reaction;
94% With hydrogenchloride; [(R)-Ru(BINAP)Cl2]2*NEt3 In methanol at 50℃; for 14h; (R)-Ethyl(-)-3-hydroxybutyrate (17) Ethyl acetoacetate 7 (3 g, 23.05 mmol) and dry methanol (25 mL) were mixed and deoxygenated with flowing nitrogen for some time. The catalyst [(R)-Ru(BINAP)Cl2]2*NEt3 (24 mg, 0.1 mol %) was added along with 2N HCl (0.04 mL, 0.1 mol %) carefully. The mixture was then transferred to a standard Parr reactor apparatus and flushed with hydrogen several times. The apparatus was charged with H2 (100 psi) and heated at 50 °C with stirring for 14 h. After completion of reaction, it was cooled and concentrated under reduced vacuo. The crude was purified by column chromatographic purification with pet ether/ethyl acetate (9:1 v/v) as eluent to obtain pure (R)-alcohol 17. Yield: 94% (2.86 g), colorless liquid; [α]20D=-46.0 (c 1.0, CHCl3) {lit.11 [α]20D=-46.0 (c 1.0, CHCl3)}; IR (CHCl3, cm-1): υmax 1458, 1636, 1734, 2935, 2978, 3441; 1H NMR (200 MHz, CDCl3): δ 1.21-1.31 (m, 6H), 2.42-2.46 (m, 2H), 3.20 (d, J = 3.8 Hz, 1H), 4.12(t, J = 7.0 Hz, 3H); 13C NMR (50 MHz, CDCl3): δ 14.1, 22.6, 43.2, 60.5, 64.2, 172.5; HRMS (ESI): calc. for [(C6H12O3)H] (M+H) 133.0865, found 133.0861.
93% With SmADH31 Enzymatic reaction; stereoselective reaction;
89% With recombinant E. coli cells coexpressing carbonyl reductase and glucose dehydrogenase on cell surface In aq. phosphate buffer; dibutyl ether at 20℃;
75% In water at 27℃; for 96h; Geotrichum candidum;
47% With Leifsonia sp. S749 cells alcohol dehydrogenase; nicotinamide adenine dinucleotide; isopropyl alcohol In phosphate buffer at 25℃; for 24h;
36% In water microbial reduction by the fungus Geotrichum candidum;
With dimethylsulfide borane complex In tetrahydrofuran at 110℃; for 0.166667h;
With Streptomyces sp. (IPV 2645)
99 % Chromat. With hydrogen In ethanol at 23 - 30℃; for 58h;
With hydrogen In ethanol for 51h; Ambient temperature; Yield given;
With dimethylsulfide borane complex; C11H17BNOP In toluene at 110℃; for 0.0833333h;
With borane-THF; (2R,4S)-2-phenyl-1,3,2-oxazaphospholidine*borane In toluene at 110℃;
With phosphate buffer; Pichia etchellsii CBS 2011 for 24h;
In dichloromethane at 55℃; for 2.7h;
In tetrahydrofuran; hydrogenchloride at 25℃; for 120h;
With hydrogen; (+)-3-[2-(diphenylphosphino-5-methoxy)phenyl]-2-(diphenylphosphino)naphtho[2,1-b]thiophene In methanol at 40℃; for 40h;
With hydrogen In methanol at 80 - 90℃;
With hydrogen; (R)-4,4'-perfluorohexylBINAP In ethanol at 50℃; for 15h;
With hydrogen In ethanol at 50℃; for 15h;
With glucose dehydrogenase; ketoreductase; NADPH In dimethyl sulfoxide at 34℃;
With hydrogen In methanol; water at 50℃; for 10h;
With Candida magnoliae carbonyl reductase; D-glucose dehydrogenase; NADPH In water; dimethyl sulfoxide at 20℃;
100 % Chromat. With hydrogen In dichloromethane at 70℃; for 24h;
With hydrogen; 1-butyl-3-methylimidazolium Tetrafluoroborate In methanol at 20℃; for 20h;
With hydrogen In ethanol; dichloromethane at 70℃; for 24h;
100 % Spectr. With hydrogen In ethanol at 50℃; for 9h;
With isopropyl alcohol In water at 25℃; for 24h;
87.6 % ee With hydrogen In ethanol at 20℃; for 6h; 23 Complex 5A-a from Example 2 (2.6 mg; 0.0025 mmol; 0.005 equiv) was placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed ethanol (2 mL) was added and the mixture was stirred for 15 minutes. Ethyl acetoacetate (64 μL; 0.5 mmol) dissolved in 2 mL of argon-degassed ethanol was added and was washed in with 1.0 mL of argon-degassed ethanol. The reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times, and the solution was assayed by chiral GC to indicate 86.2% conversion to ethyl (R)-3-hydroxybutyrate with 87.6% ee.
81.7 % ee With hydrogen In ethanol at 20℃; for 6h; 29 Complex 5A-g from Example 9 (2.8 mg; 0.0025 mmol; 0.005 equiv) was placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed ethanol (2 mL) was added and the mixture was stirred for 15 minutes. Ethyl acetoacetate (64 μL; 0.5 mmol) dissolved in 2 mL of argon-degassed ethanol was added and was washed in with 1.0 mL of argon-degassed ethanol. The reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times, and the solution was assayed by chiral GC to indicate 100% conversion to ethyl (R)-3-hydroxybutyrate with 81.7% ee.
92.7 % ee With hydrogen In ethanol at 20℃; for 6h; 32 Complex 5A-i from Example 11 (2.8 mg; 0.0025 mmol; 0.005 equiv) was placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed ethanol (2 mL) was added and the mixture was stirred for 15 minutes. Ethyl acetoacetate (64 μL; 0.5 mmol) dissolved in 2 mL of argon-degassed ethanol was added and was washed in with 1.0 mL of argon-degassed ethanol. The reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times, and the solution was assayed by chiral GC to indicate 33.5% conversion to ethyl (R)-3-hydroxybutyrate with 92.7% ee.
95.4 % ee With hydrogen In ethanol at 20℃; for 6h; 36 Complex 5A-j from Example 12 (2.8 mg; 0.0025 mmol; 0.005 equiv) was placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed ethanol (2 mL) was added and the mixture was stirred for 15 minutes. Ethyl acetoacetate (64 μL; 0.5 mmol) dissolved in 2 mL of argon-degassed ethanol was added and was washed in with 1.0 mL of argon-degassed ethanol. The reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times, and the solution was assayed by chiral GC to indicate 100% conversion to ethyl (R)-3-hydroxybutyrate with 95.4% ee.
94.0 % ee With hydrogen In ethanol at 20℃; for 6h; 46 Complex 5A-k from Example 13 (3.0 mg; 0.0025 mmol; 0.005 equiv) was placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed ethanol (2 mL) was added and the mixture was stirred for 15 minutes. Ethyl acetoacetate (64 μL; 0.5 mmol) dissolved in 2 mL of argon-degassed ethanol was added and was washed in with 1.0 mL of argon-degassed ethanol. The reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times, and the solution was assayed by chiral GC to indicate 59.2% conversion to ethyl (R)-3-hydroxybutyrate with 94.0% ee.
92.5 % ee With hydrogen In ethanol at 20℃; for 6h; 52 Complex 5A-l from Example 14 (2.8 mg; 0.0025 mmol; 0.005 equiv) was placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed ethanol (2 mL) was added and the mixture was stirred for 15 minutes. Ethyl acetoacetate (64 μL; 0.5 mmol) dissolved in 2 mL of argon-degassed ethanol was added and was washed in with 1.0 mL of argon-degassed ethanol. The reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times, and the solution was assayed by chiral GC to indicate 100% conversion to ethyl (R)-3-hydroxybutyrate with 92.5% ee.
91.6 % ee With hydrogen In ethanol at 20℃; for 6h; 55 Complex 5A-n from Example 16 (2.7 mg; 0.0025 mmol; 0.005 equiv) was placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed ethanol (2 mL) was added and the mixture was stirred for 15 minutes. Ethyl acetoacetate (64 μL; 0.5 mmol) dissolved in 2 mL of argon-degassed ethanol was added and was washed in with 1.0 mL of argon-degassed ethanol. The reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times, and the solution was assayed by chiral GC to indicate 100% conversion to ethyl (R)-3-hydroxybutyrate with 91.6% ee.
92.7 % ee With hydrogen In ethanol at 20℃; for 6h; 58 Complex 5A-o from Example 17 (2.7 mg; 0.0025 mmol; 0.005 equiv) was placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed ethanol (2 mL) was added and the mixture was stirred for 15 minutes. Ethyl acetoacetate (64 μL; 0.5 mmol) dissolved in 2 mL of argon-degassed ethanol was added and was washed in with 1.0 mL of argon-degassed ethanol. The reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times, and the solution was assayed by chiral GC to indicate 99.8% conversion to ethyl (R)-3-hydroxybutyrate with 92.7% ee.
86.7 % ee With hydrogen In ethanol at 50℃; for 15h; 10 Example 10: (U)-Ethyl 3-hydroxybutyrateIn a 15 mL autoclave under argon atmosphere RuCls (1.5 mg, 0.007 mmol), (-)-ligand Ib(4.3 mg, 0.007 mmol) and ethyl acetoacetate (0.15 g, 1.1 mmol) is dissolved in degassedethanol (7 mL). After flushing the autoclave with argon hydrogenation is carried out during15 h at 50°C and at 4 bar hydrogen pressure. After cooling to room temperature thereaction solution is directly analyzed by GC for conversion (column: HP-101 25 m /0.2 mm) and, after derivatization with trifluoroacetic acid anhydride, enantiomeric excess(column: Lipodex-E 25 m / 0.25 mm). Conversion is 98.3% at an ee of 86.7%.
99 % ee With (R)-5,5'-perfluorohexylBINAP; hydrogen In ethanol at 50℃; for 15h; 11 In order to evaluate the activities of these novel ligands and the influence of the perfluoro chains, the corresponding metal complexes were prepared by reaction with [RuCl2(benzene)]2 in accordance with the general procedure described by Noyori et al. [Kitamura, M.; Tokunaga, M.; Ohkuma, T.; Noyori, R. Tetrahedron Lett. 1991, 32, 4163]. The complexes were tested for the catalytic hydrogenation of several β-keto esters. The results are given in the following table: Substrate/ Ex. catalyst Conversion e.e. ref. Ligand Complex R in mol (%) (%) 10 ex 8[RuCl2(benzene)]2 Me 1000 100 99 11 ex 8[RuCl2(benzene)]2 Et 2000 100 99
83 - 90 % ee With hydrogen In ethanol at 50℃; 14 Degassed anhydrous ethanol is added to the reactor in which the catalyst has just been prepared. The substrate is then added (in a defined catalyst/substrate ratio). The reactor is placed in an autoclave under a hydrogen pressure of 40 bar and at 50° C. Stirring is maintained overnight. The reactor is recovered and then centrifuged. The supernatant solution is recovered and then analyzed by gas chromatography. The determination of the enantiomeric excess is performed by chiral gas chromatography on a Lipodex A 25 m×0.25 mm column. The results obtained are given in the following table: Catalyst Substrate/catalyst Conversion e.e. (5,5'-polyNAP) in mol (%) (%) 5,5' 1000 100 83 5,5' 500 100 85 5,5' (recycled) 500 100 90 The hydrogenation of ethyl acetoacetate leads to ethyl 3-hydroxybutyrate.
With dichloro(benzene)ruthenium(II) dimer; (R)-2,2'-bis(diphenylphosphanyl)-7,7'-dipropoxy-1,1'-binaphthalenyl; hydrogen In ethanol at 50℃; for 12h; optical yield given as %ee; enantioselective reaction;
With ketoreductase from Lactobacillus kefir KefC; NADPH at 20℃; aq. buffer; Enzymatic reaction; optical yield given as %ee; enantioselective reaction;
86.7 % ee With (-)-6-dicyclohexylphosphanyl-2'-diphenylphosphino-2-methoxy-1,1'biphenyl; hydrogen In ethanol at 50℃; for 15h; 18 In a 15 mL autoclave under argon atmosphere RuCl3 (1.5 mg, 0.007 mmol), (-)-ligand Ib (4.3 mg, 0.007 mmol) and ethyl acetoacetate (0.15 g, 1.1 mmol) is dissolved in degassed ethanol (7 mL). After flushing the autoclave with argon hydrogenation is carried out during 15 h at 50°C and at 4 bar hydrogen pressure. After cooling to room temperature the reaction solution is directly analyzed by GC for conversion (column: HP-101 25 m /0.2 mm) and, after derivatization with trifluoroacetic acid anhydride, enantiomeric excess (column: Lipodex-E 25 m / 0.25 mm). Conversion is 98.3% at an ee of 86.7%.
86.7 % ee With hydrogen In ethanol at 50℃; for 15h; 14 Example 14: CR)-Ethyl 3-hydroxybutyrate; In a 15 mL autoclave under argon atmosphere RuCls (1.5 mg, 0.007 mmol), (-)-ligand Ib(4.3 mg, 0.007 mmol) and ethyl acetoacetate (0.15 g, 1.1 mmol) is dissolved in degassedethanol (7 mL). After flushing the autoclave with argon hydrogenation is carried out during15 h at 50°C and at 4 bar hydrogen pressure. After cooling to room temperature thereaction solution is directly analyzed by GC for conversion (column: HP-101 25 m /0.2 mm) and, after derivatization with trifluoroacetic acid anhydride, enantiomeric excess(column: Lipodex-E 25 m / 0.25 mm). Conversion is 98.3% at an ee of 86.7%.
With isopropyl alcohol at 37℃; for 3h; aq. acetate buffer; Enzymatic reaction; optical yield given as %ee; enantioselective reaction;
With hydrogen In methanol Inert atmosphere;
With hydrogen In methanol at 50℃; for 24h; Autoclave; optical yield given as %ee; enantioselective reaction;
With recombinant stereospecific carbonyl reductase 1 from Candida parapsilosis; NAD In aq. phosphate buffer at 30℃; for 6h;
80 %Chromat. With Aspergillus flavus strain 4 at 35℃; for 72h;
98.8 %Chromat. With hydrogen In ethanol at 60℃; for 6h; Inert atmosphere; Autoclave; enantioselective reaction; 2.4. Catalytic hydrogenation General procedure: Catalytic hydrogenation reactions were carried out in a 50 mL autoclave equipped with a magnetic bar. The reaction temperature was controlled by an electric heater and maintained at a set temperature. All reaction temperatures were 60 ◦C, and the hydrogen pressure was set at 40 bar. Prior to use, all substrates and solvents were degassed at reduced pressure with an aspirator. Under inert atmosphere conditions, catalyst, degassed solvent, and substrate were introduced sequentially into the reactor. The reactor was connected to a hydrogenation apparatus and purged with hydrogen (3 bar) five times before stirring was initiated. The reaction was initiated by introducing hydrogen at a pressure of 40 bar. Samples were obtained at predetermined time intervals from the reaction mixture to determine the reaction rate and enantioselectivity. The products were analyzed by gas chromatography (HP 6890) using a Rtx-1701 column. Enantiomeric excess was determined by GC using a Chiraldex G-TA column.
> 99 % ee With D-glucose; D-glucose dehydrogenase; Pichia guilliermondii; nicotinamide adenine dinucleotide phosphate In aq. phosphate buffer; dimethyl sulfoxide at 30℃; for 12h; Enzymatic reaction; enantioselective reaction;
With hydrogenchloride; dichloro-di-μ-chloro-bis(R-2,2'-bis(diphenylphosphine)-1,1'-binaphtyl)diruthenium(II); hydrogen; triethylamine In methanol; water at 50℃; for 16h; Inert atmosphere; 9 Exam pie 9: (R)-Ethyl (-)-3-hydroxybutyrate, (43) [00059] Ethyl acetoacetate (7.5g) and dry methanol (25 mL) were mixed and deoxygenated with flowing nitrogen for five minutes. The catalyst [(R)-Ru(BINAP)C12]2 NEt3 (0.1 mol %) was added along with 2N HCI (0.1 mol %). The mixture was transferred to a standard Parr reactor apparatus and flushed by evacuating and refilling with hydrogenseveral times. The apparatus was heated at 50 °C with stirring under 100 psi of hydrogen for 16 h. After completion of reaction (monitored by TLC) the reaction was cooled and concentrated under reduced pressure. The residue was subjected to column chromatographic purification with petroleum ether/ethyl acetate (9:1 v/v) to get pure (R)alcohol 43 as a colorless liquid.[a]025 -46.0 (c 1.0, CHC13); lit.” [a]025 -46.0 (c 1.0, CHCI3); 98% ee (Mosher ester); IR (CHCI3, cm’) 3441.7, 2978.6, 2935.7, 1734.0, 1636.1, 1458.1; ‘H NMR (200 MHz, CDCI3): ö 4.12-4.22 (m, 3H), 3.20 (d, J 3.8 Hz, 1H), 2.42-2.45 (m, 2H), 1.21-1.31 (m, 6H); ‘3C NMR (50 MHz, CDCI3): ö 172.5,64.2, 60.5, 43.2, 22.6, 14.1. Analysis: C6H,203 requires C, 54.53; H, 9.15; found C, 54.56; H, 9.35%.
~ 95 % ee With baker's yeast In water; glycerol at 20℃; for 72h; Microbiological reaction; enantioselective reaction;
94 % ee With hydrogen; acetic acid In tetrahydrofuran at 100℃; for 20h; Autoclave; enantioselective reaction; General procedure: Nickel powders (5 μm) purchased from Aldrich were directly subjected to chiral modification without any pretreatment, such as hydrogen activation. The chiral modification was performed under the conditions optimized previously for this type of catalyst.26 Thus, the non-activated nickel powders (0.5 g) were immersed in an aqueous solution (50 cm3) of (R,R)-tartaric acid (0.5g) and NaBr (2.0 g) at 100 °C, the pH of which was pre-adjusted to 3.2 with an aqueous 1M NaOH solution. NaBr was added to the modification solution to block the non-enantiodifferentiating sites of tartaric acid/Ni catalyst, thus preventing the generation of racemic products.39 After immersion for 1 h, the modification solution was removed by decantation and the catalyst was successively washed once with deionized water (10 cm3), twice with methanol (25 cm3), and twice with tetrahydrofuran (THF) (10 cm3). The modified catalyst was added to a mixture of alkyl acetoacetate (43 mmol for methyl ester and 21.5 mmol for other esters), acetic acid (0.1g), and THF (10 cm3) placed in an autoclave equipped with a magnetically coupled mechanical stirrer. The hydrogenation was run for 20h at 100 or 110 °C and at a hydrogen pressure of 9MPa. The hydrogenation product, a mixture of alkyl (R)- and (S)-3-hydroxybutyrates, was isolated from the reaction mixture by distillation. The conversion was determined by gas-liquid chromatography (GLC) on a GL Science model GC-4000 equipped with a CP Chirasil DEX-CB capillary column (0.25 mm × 25 m) at 90 °C, while the enantioselectivity was determined by chiral GLC after acetylation of the reaction product using acetyl chloride and pyridine. A portion of the acetylated sample was subjected to the chiral GLC analysis on a CP Chirasil DEX-CB column (0.25 mm × 25 m) operated at 90 °C. The ee value was calculated from the peak integration of the corresponding enantiomer peaks. The reproducibility of the ee value was found to be within ±2%.
93 % ee With dichloro(benzene)ruthenium(II) dimer; hydrogen In methanol at 52℃; for 24h; enantioselective reaction;
With hydrogenchloride; [RuCl2-((R)-binap)]*NEt3; hydrogen In methanol; water at 50℃; for 16h; Inert atmosphere; 9 (R)-Ethyl(-)-3-hydroxybutyrate, (43) Ethyl acetoacetate (7.5 g) and dry methanol (25 mL) were mixed and deoxygenated with flowing nitrogen for five minutes. The catalyst [(R)-Ru(BINAP)Cl2]2NEt3 (0.1 mol %) was added along with 2N HCl (0.1 mol %). The mixture was transferred to a standard Parr reactor apparatus and flushed by evacuating and refilling with hydrogen several times. The apparatus was heated at 50° C. with stirring under 100 psi of hydrogen for 16 h. After completion of reaction (monitored by TLC) the reaction was cooled and concentrated under reduced pressure. The residue was subjected to column chromatographic purification with petroleum ether/ethyl acetate (9:1 v/v) to get pure (R)-alcohol 43 as a colorless liquid. [α]D25 -46.0 (c 1.0, CHCl3); lit. [α]D25 -46.0 (c 1.0, CHCl3); 98% ee (Mosher ester); IR (CHCl3, cm-1) 3441.7, 2978.6, 2935.7, 1734.0, 1636.1, 1458.1; 1H NMR (200 MHz, CDCl3): δ 4.12-4.22 (m, 3H), 3.20 (d, J=3.8 Hz, 1H), 2.42-2.45 (m, 2H), 1.21-1.31 (m, 6H); 13C NMR (50 MHz, CDCl3): δ 172.5, 64.2, 60.5, 43.2, 22.6, 14.1. Analysis: C6H12O3 requires C, 54.53; H, 9.15. Found C, 54.56; H, 9.35%.
> 99 % ee With glucose dehydrogenase; alpha-D-glucopyranose; BgADH1 enzyme; nicotinamide adenine dinucleotide phosphate In water at 30℃; Enzymatic reaction; enantioselective reaction;
> 99 % ee With aldo-keto reductase CaAKR; NADH In aq. phosphate buffer at 30℃; for 10h; Enzymatic reaction; enantioselective reaction; 2.8 Substrate specificity General procedure: The bioreduction was performed in 1.5 mL Eppendorf tubes containing 200 mmol/L potassium phosphate buffer (pH 7.0), 1 mmol/L of each substrate, 0.5 mmol/L NADH, and 1 mg/mL purified CaAKR in a total volume of 1.0 mL, shaking for 10 h at 30 °C. The reaction mixture was extracted twice with an equivalent volume of 300 μL ethyl acetate. The extracts were combined, dried with anhydrous sodium sulfate. The concentrations for each product were determined by GC or HPLC analysis.
94 % ee With hydrogen; sodium bromide In tetrahydrofuran; methanol at 99.84℃; for 20h; Autoclave; enantioselective reaction;
99.9 % ee With recombinant alcohol dehydrogenase from Stenotrophomonas maltophilia SmADH2; isopropyl alcohol; NADH In aq. phosphate buffer at 30℃; Green chemistry; Enzymatic reaction; stereoselective reaction;
95.1 % ee With dichloro(benzene)ruthenium(II) dimer; hydrogen In methanol at 50℃; for 20h; Inert atmosphere; Autoclave; enantioselective reaction;
99.6 % ee With D-Glucose; cobalt(II); BaSDR1 reductase variant Q139G; NADH In aq. phosphate buffer at 35℃; Enzymatic reaction; enantioselective reaction;

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  • 15
  • [ 141-97-9 ]
  • [ 24915-95-5 ]
  • [ 56816-01-4 ]
YieldReaction ConditionsOperation in experiment
85% With citrate-phosphate-borate buffer for 24h; Ambient temperature; baker's yeast immobilized in calcium alginate; Title compound not separated from byproducts;
70% With Convolvulus sepium for 120h; aq. phosphate buffer; optical yield given as %ee;
26% Enzymatic reaction; 7 Incubation time and temperature depend upon the substrate and source of the enzymes used.
1: 10% 2: 6% With cyanobacterium Synechocystis sp. PCC 6803 Williams strain, cultivated at 25 °C with fluorescent lamp about 10 days In water; dimethyl sulfoxide at 25℃; for 24h; Irradiation; 4. General procedure for the asymmetric reduction of β-keto esters 1a-f using cyanobacterium Synechocystis sp. PCC 6803. General procedure: 6 mL of a solution of β-keto esters 1a-f in DMSO (10 mg/mL) was added to 6 mL of the cell suspension. The mixture was shook at 25°C for 3-24 h under illumination of LED light (red or blue, 0.5-20 mmol photons m-2 s-1) or in the dark. After the reaction, the cells were separated off by centrifugation and the supernatant was extracted with diethyl ether containing naphthalene as an internal standard. The products 2a-f were analyzed by gas chromatography. The yields were determined on the basis of the standard calibration curve of the authentic samples. The reaction degree and enantioselectivity were indicated by the yield and the ee value, respectively, calculated with the following formulae: Yield (%) = Calcohol / (Cketone + Calcohol) ee (%) = 100 × (CR - CS)/(CR + CS) where Ckeone is the final substrate concentration, Calcohol is the final product concentration, CR is the final R-form product concentration, and Cs is the final S-form product concentration. The results were summarized in Table 1.
In water bakers' yeast; addition of MgCl2; immobilization of bakers' yeast by magnesium alginate;
With D-glucose; bakers' yeast; allyl alcohol In water at 30℃; for 24h; effect and amount of added allyl alcohol, stereoselectivity;
With hydrogen In ethanol enanthioselectivity ca. 10percent; electrolysis; effect of aq. NaOH;
With L-Tartaric acid; hydrogen at 50℃; for 2h; other catalysts, temperature, reaction time;
With L-Tartaric acid; hydrogen at 80℃; other catalysts, temperature, reaction time, pressure;
With hydrogen at 100℃; for 3.5h; rate of hydrgenation; optical yield; influence of the modifiers (amino acids); pH 5.1;
With citrate-phosphate-borate buffer for 24h; Ambient temperature; baker's yeast immobilized in calcium alginate; pH effect on the enantiospecificity ; also for ethyl benzoylacetate;
With hydrogen at 90℃; catalyst composition dependence;
With L-glutamic acid; hydrogen other reagents (chiral amino acids), other catalyst;
With D-glucose In ethanol; water at 25℃; for 48h; yeast Saccharomyces cerevisiae IFO 0565; yeast-mediated biochemical reduction of 3-oxoalkanoic esters, stereoselectivity, enantiomeric excess;
With baker's yeast; resin XAD 1180 In water at 28℃; other absorbing resins; also organic solvents;
With sodium tetrahydroborate; L-Tartaric acid In tetrahydrofuran at -20℃; for 17h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With D-glucose; bakers' yeast; allyl alcohol In water at 30℃; for 24h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
In ethanol for 24h; growing cultures of Aspergillus niger IPV283; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With hydrogen In tetrahydrofuran; acetic acid at 85℃; for 5h; Title compound not separated from byproducts;
With hydrogen In methanol; dichloromethane at 50℃; for 14h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With Ru<(S)-Ph,Ph-oxoProNOP>(OCOCH3)2; hydrogen In dichloromethane at 20℃; for 168h; Title compound not separated from byproducts;
In water at 25 - 28℃; for 144h; sugar, baker's yeast; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
at 72℃; pH 6.9; Thermoanaerobium brockii; Title compound not separated from byproducts;
With D-glucose; bakers' yeast In water at 30℃; for 24h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
at 72℃; for 24h; cells of Thermoanaerobium brockii; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
In water; Petroleum ether for 24h; Ambient temperature; freeze-dried yeast; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
In ethanol for 24h; growing cultures of Geotrichum candidum CBS10912; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With potassium hydroxide 1.) EtOH, 25 deg. C, 20 h, 2.) baker's yeast, fermentation medium, 25 deg C, 2 d; Yield given. Multistep reaction. Title compound not separated from byproducts;
With D-glucose In water at 30℃; for 24h; raw bakers' yeast; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With D-glucose In ethanol; water at 25℃; for 48h; bakers' yeast; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
In water baker's yeast;
With RuCl2[(S)-BINAP]; DOWEX-50 resin; hydrogen In ethanol at 130℃; for 10h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With ammonium sulfate; potassium dihydrogenphosphate; ordinary baker's yeast; magnesium sulfate; Sucrose for 24h; other 3-oxo esters; other fermenting baker's yeast preparations; also or without var. co-substrates; var. pH's, conc., and reaction times; var. preincubation times; aerobic and anaerobic conditions;
With baker's yeast; allyl alcohol; Sucrose for 22h; Ambient temperature; Title compound not separated from byproducts;
With baker's yeast for 24h; Ambient temperature; Title compound not separated from byproducts;
With hydrogen In ethanol at 20 - 60℃;
With hydrogen In ethanol at 20℃;
With hydrogen In ethanol at 50℃; Title compound not separated from byproducts;
With RuCl[(-)-N,N'-Me2-3,3'-bis(Ph2P)-2,2'-biindole](p-cymene); hydrogen In methanol; water at 10℃; for 30h;
With diiodo(p-cymene)ruthenium(II) dimer; (S(p),S(p))-2,2''-bis(diphenylphosphino)-1,1''-biferrocene; hydrogen In hydrogenchloride; ethanol at 80℃; for 16h; Title compound not separated from byproducts;
With baker's yeast In water Title compound not separated from byproducts;
With hydrogen at 40℃; for 3.5h;
With immibilized baker's yeast; 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate; calcium alginate In methanol; water at 33℃; for 72h;
With hydrogen; (+)-3-[2-(diphenylphosphino-5-methoxy)phenyl]-2-(diphenylphosphino)naphtho[2,1-b]thiophene In methanol at 40℃; for 1.83333h;
With chiral 1,5-diphenylphosphanylferrocene compound; hydrogen bromide; hydrogen In methanol at 50℃; for 9h;
With Daucus carota root In water at 20℃; for 58h; Title compound not separated from byproducts;
With baker's yeast for 96h; Title compound not separated from byproducts;
With hydrogen In ethanol at 30℃; for 21.5h; Title compound not separated from byproducts;
With hydrogen In ethanol at 30℃; for 16.5h; Title compound not separated from byproducts;
With D-glucose; immobilized bakers' yeast In various solvent(s) at 30℃; for 41h; Title compound not separated from byproducts;
With hydrogen In water at 50℃; for 15h; Title compound not separated from byproducts;
With Rhizopus arrhizus culture In ethanol at 27℃; for 192h; Title compound not separated from byproducts;
With hydrogen In ethanol at 70℃; for 1440h; Title compound not separated from byproducts;
With D-glucose; D-glucose dehydrogenase; recombinant ketoreductase In phosphate buffer at 25℃;
With RuCl[(-)-N,N'-Me2-3,3'-bis(Ph2P)-2,2'-biindole](p-cymene); hydrogen In methanol; water at 10℃; for 30h;
With potassium phosphate buffer; Rhodotorula sp. AS22241 at 30℃; for 4h; Title compound not separated from byproducts;
With (11bS, 11'bS)-4,4'-(oxydi-2,1-phenylene)bis-dinaphtho[2,1-d:,1',2'-f][1,3,2]dioxaphosphepin; hydrogen In ethanol; dichloromethane at 60℃; for 20h;
With 1,1-dicyclohexyl-2,2-diphenyldiphosphane; hydrogen In ethanol at 50℃; for 15h;
With hydrogen In ethanol at 20℃; for 6h;
With D-glucose; D-glucose dehydrogense; Pyrococcus furiosus alcohol dehydrogenase In dimethyl sulfoxide at 37℃; Title compound not separated from byproducts;
With D-glucose; D-glucose dehydrogenase; NADPH In dimethyl sulfoxide at 20℃; Title compound not separated from byproducts.;
71.6 % ee With hydrogen In ethanol at 20℃; for 6h; 27 Complex 5A-c from Example 5 (2.6 mg; 0.0025 mmol; 0.005 equiv) was placed in a reaction vessel, which was pressurized with argon and vented five times. Argon-degassed ethanol (2 mL) was added and the mixture was stirred for 15 minutes. Ethyl acetoacetate (64 μL; 0.5 mmol) dissolved in 2 mL of argon-degassed ethanol was added and was washed in with 1.0 mL of argon-degassed ethanol. The reaction mixture was pressurized with argon and vented five times and then pressurized to 20.7 barg (300 psig) with hydrogen and stirred at ambient temperature for 6 hours. The vessel was vented, then pressurized with argon and vented five times, and the solution was assayed by chiral GC to indicate 84.8% conversion to ethyl (R)-3-hydroxybutyrate with 71.6% ee.
With hydrogen In ethanol at 50℃; for 8h; Title compound not separated from byproducts.;
With Kluyveromyces marxianus Enzymatic reaction; optical yield given as %ee;
With Saccharomyces cerevisiae 40 Enzymatic reaction; optical yield given as %ee;
With ketoreductase from Streptomyces coelicolor StaC; NADH at 20℃; aq. buffer; Enzymatic reaction; optical yield given as %ee; enantioselective reaction;
With hydrogenchloride; diiodo(p-cymene)ruthenium(II) dimer; (S(p),S(p))-2,2''-bis(diphenylphosphino)-1,1''-biferrocene; hydrogen In ethanol; water at 80℃; for 19h; Autoclave; optical yield given as %ee; enantioselective reaction;
With hydrogen In methanol at 20℃; for 16h; 166 A solution of [(cod)RuX2]x (10 μmol) (prepared as above) and the L* (10 μmol) in acetone (1 ml) is stirred for 30 min at room temperature then concentrated. A solution of the substrate (1 mmol) in MeOH (2 ml) is added and the solution is hydrogenated as indicated.
With L-Tartaric acid; hydrogen; nickel; acetic acid In ethyl acetate at 140℃; for 13h; enantioselective reaction;
With Saccharomyces cerevisiae at 30℃; for 16h; aq. buffer; optical yield given as %ee; enantioselective reaction;
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; sodium formate; (2S)-N-phenylpyrrolidine-2-carboxamide In water at 30℃; for 16h; optical yield given as %ee; enantioselective reaction;
With D-glucose; glucose dehydrogenase from Bacillus subtilis; β-ketoacyl-ACP reductase from Bacillus sp. ECU0013; NADP at 30℃; for 12h; aq. phosphate buffer; Enzymatic reaction; optical yield given as %ee;
With hydrogen; cinchonidine; acetic acid In water at 20℃; Autoclave; enantioselective reaction;
With [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II); hydrogen In methanol at 60℃; for 20h; Optical yield = 81 %ee; enantioselective reaction; General procedure for Ru-catalysed asymmetric hydrogenation of MAA in IL/MeOH systems and for catalyst recycling General procedure: Typically, the preceding catalysts 6-Ru (0.0031 mmol) or 7-Ru(0.0031 mmol) were dissolved in IL/MeOH (IL: 1 g, MeOH: 1 mL)under an argon atmosphere. The MAA (36 mg, 0.31 mmol) wereadded to the solution of catalyst. Next, the reaction mixture wastransferred to a 60 mL autoclave. The hydrogenation was carriedout under 4 MPa pressure of hydrogen at 60 ◦C for 20 h. After releasingthe hydrogen, the reaction mixture was transferred to a Schlenktube under an argon atmosphere. Next the MeOH was removedunder reduced pressure and ether was added to extract the product(1 mL×2). The top solvent layer was removed by a syringe forGC analysis, and the new substrate and MeOH was added to the ILfor next catalyst recycling
With bis(1,5-cyclooctadiene)diiridium(I) dichloride; (R)-N-(3-methylpyridine-2-methyl)-7-bis-(3,5-di-tert-butylphenyl)phosphino-7′-amino-1,1′-spirodihydroindane; potassium <i>tert</i>-butylate; hydrogen In ethanol at 20℃; for 0.5h; Inert atmosphere; Sealed tube; Overall yield = 100 %; 11 Example 11: Application of chiral spiro-pyridylamidophosphine ligand (R)-Ii (prepared in Example 9) in the asymmetric catalytic hydrogenation reaction of carbonyl compounds Example 11: Application of chiral spiro-pyridylamidophosphine ligand (R)-Ii (prepared in Example 9) in the asymmetric catalytic hydrogenation reaction of carbonyl compounds[0059] [0060] Under the protection of nitrogen atmosphere, 0.5 mg (0.74µmol) [Ir(COD)]Cl2, 1.2 mg (1.6µmol) (R)-Ii were added to the inner hydrogenation tube. Subsequently, 1 ml absolute ethyl alcohol was added and stirred for 1 h at room temperature. The inner reaction tube was placed into the hydrogenation reactor. After substitution by hydrogen, the reaction was stirred for 1 h at a hydrogen pressure of 1 atmosphere. The reactor was opened, and 7.5-150 mmol substrate (solid substrate, added after dissolved by ethanol) was added, followed by 0.05-25 mmol potassium tert-butoxide solution in ethanol (0.5 ml (0.1 mmol/mL)-25 ml (1 mmol/mL)) added with a syringe. The reactor was sealed, and hydrogen was filled to a pressure of 8-10 atm, and the reaction was stirred under the hydrogen pressure at room temperature for a while ranging from 10 minutes to 24 hours. After the hydrogenation was finished, the reaction solution was filtered through a short silica gel column to remove the catalyst, and the conversion rate and yield of the reaction were analyzed by gas chromatography or nuclear magnetic resonance (NMR); and the optical purity of the product was analyzed by gas chromatography or high performance liquid chromatography. The results of the hydrogenation experiments were listed in Table 1.
With reductase from Rhodococcus sp. ECU1014; NADH In aq. phosphate buffer Enzymatic reaction; Optical yield = 7.9 %ee; Enzyme assays General procedure: The reductase activity was analyzed spectrophotometrically at 30°C by monitoring the decrease in the absorbance of NADH at 340nm. The standard analysis mixture (1mL) was composed of 100mM Na2HPO4-NaH2PO4 buffer (pH 6.0), 2.0mM ketoesters, 0.1mM NADH and an appropriate amount of enzyme. One unit was defined as the amount of enzyme leading to the consumption of 1μmol of NADH per min.
34 % ee With hydrogen In tetrahydrofuran at 25℃; Autoclave; stereoselective reaction;
33 % ee With hydrogen In tetrahydrofuran at 25℃; Autoclave; stereoselective reaction;
85 % ee With Sucrose In water at 25 - 30℃; Overall yield = 76 %; Overall yield = 31 g; enantioselective reaction;
86 % ee With dichloro[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium(II); hydrogen In ethanol at 80℃; for 8h; Autoclave; Overall yield = 95 %; Overall yield = 6.3 g; 1.21 (R,E)-4-((tert-Butyldimethylsilyl)oxy)-4-((3aR,4R,7S,7aR)-7-((4R,5S,E)-5-(methoxymethoxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)-3-methylbut-2-enoic acid (6) 4.1.21 (S)-Ethyl 3-hydroxybutanoate (25) A 100-mL, parr hydrogenation vessel was charged with Ethyl acetoacetate (6.5 g, 50 mmol) and degassed Ethanol (70 mL). To this mixture was added the in situ prepared [(S)-2,2' Bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium(II) complex (0.1 mol%, 43 mg, 0.05 mmol) in degassed Ethanol (5 mL) under an argon. The hydrogenation vessel was attached to a hydrogen source and hydrogenation was carried out at 50 psig H2 and 80 °C for 8 h. After the reaction mixture was allowed to cool to room temperature, the stop valve was opened, excess hydrogen was carefully bled off, and the apparatus was disassembled. The resulting orange solution was poured into a 250 mL, round-bottomed flask, and the hydrogenation vessel was rinsed with dichloromethane (3 * 30 mL). The solvent was removed by a rotary evaporator, and the residue was distilled to give hydroxy ester 25 with er 93:7 (6.3 g, 47.5 mmol) in 95% yield (bp 72 °C, 12 mm Hg). TLC: Rf = 0.3 (ethyl acetate: hexane, 30:70); [α]25D = +38° (c = 1.0, CHCl3); IR (neat) νmax: 3449, 2979, 2938, 1732, 1377, 1188 cm -1; 1H NMR (500 MHz, CDCl3): δ 4.18-4.10 (m, 3H), 2.94-2.68 (bs, OH), 2.43 (dd, J = 16.8, 4.0 Hz, 1H), 2.37 (dd, J = 16.8, 8.9 Hz, 1H), 1.27 (t, J = 6.9 Hz, 3H), 1.20 (d, J = 6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3): δ 172.6, 64.1, 60.5, 42.8, 22.3, 14.0; MS (ESI): 133 [M+H]+; HRMS (ESI): m/z Calcd. for C6H13O3: 133.0859, found 133.0860.
31 % ee With glucose dehydrogenase; D-glucose; NADP<SUP>+</SUP>; carbonyl reductase LbCR In aq. phosphate buffer at 30℃; for 12h; Enzymatic reaction; enantioselective reaction;
43.4 % ee With D-Glucose; cobalt(II); BaSDR1 reductase variant Q139V/Q237L; NADH In aq. phosphate buffer at 35℃; Enzymatic reaction; enantioselective reaction;
76.1 % ee With D-Glucose; cobalt(II); BaSDR1 reductase variant Q242E; NADH In aq. phosphate buffer at 35℃; Enzymatic reaction; enantioselective reaction;
27 % ee With cyanobacterium Synechocystis sp. PCC 6803 In water at 25℃; for 24h; Irradiation; Enzymatic reaction; Overall yield = 16 percentChromat.; stereoselective reaction; 4. General procedure for the asymmetric reduction of β-keto esters 1a-c using cyanobacterium Synechocystis sp. PCC 6803 General procedure: 6 μL of a solution of β-keto esters 1a-c in DMSO (10 mg/mL) was added to 6 mL of the cell suspension containing an organic solvent (0-5%). The mixture was shook at 25°C for 24 h under illumination with LED light (red, 10 μmol photons m-2 s-1) or in the dark. After the reaction, the cells were separated off by centrifugation and the supernatant was extracted with diethyl ether containing naphthalene as an internal standard. The products 2a-c were analyzed by gas chromatography. The yields were determined on the basis of the standard calibration curve of the authentic samples. The reaction degree and enantioselectivity were indicated by the yield and the ee value, respectively, calculated with the following formulae: Yield (%) = Calcohol / (Cketone + Calcohol) ee (%) = 100 × (CR - CS)/(CR + CS) where Cketone is the final substrate concentration, Calcohol is the final product concentration, CR is the final R-form product concentration, and CS is the final S-form product concentration.

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