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CAS No. : | 10172-89-1 | MDL No. : | MFCD00002664 |
Formula : | C11H13NO3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | CBQJSKKFNMDLON-SNVBAGLBSA-N |
M.W : | 207.23 | Pubchem ID : | 101184 |
Synonyms : |
|
Num. heavy atoms : | 15 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.27 |
Num. rotatable bonds : | 5 |
Num. H-bond acceptors : | 3.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 55.41 |
TPSA : | 66.4 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.9 cm/s |
Log Po/w (iLOGP) : | 1.23 |
Log Po/w (XLOGP3) : | 0.93 |
Log Po/w (WLOGP) : | 0.82 |
Log Po/w (MLOGP) : | 1.17 |
Log Po/w (SILICOS-IT) : | 1.22 |
Consensus Log Po/w : | 1.07 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.56 |
Log S (ESOL) : | -1.68 |
Solubility : | 4.36 mg/ml ; 0.0211 mol/l |
Class : | Very soluble |
Log S (Ali) : | -1.91 |
Solubility : | 2.55 mg/ml ; 0.0123 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -2.62 |
Solubility : | 0.499 mg/ml ; 0.00241 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.81 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 37℃; for 0.166667h; D-aminocyclase from Alcaligenes denitrificans DA181, pH 7.8, bovine serum albumin; | ||
With hydrogenchloride | ||
With hydrogenchloride |
With hydrogen bromide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide | ||
at 0 - 4℃; for 3h; | ||
With sodium hydroxide In water at 0 - 25℃; for 0.5h; | 17 Preparation of N-Acetyl-D-phenylalanine To a stirred solution D-phenylalanine (20gms) in water (120 ml) at 0 to 5°C, aq. sodium hydroxide solution was added maintain its pH 11-12. To this basic amino acid solution, acetic anhydride (37 ml) and aq. sodium hydroxide were simultaneously added at a temperature between 10-15°C. After completion of addition, reaction mass was kept under stirring for 30 minutes at 20 to 25°C, then the reaction mixture was acidified to pH 1 with concentrated HC1. The resulting ppt was filtered, re- crystallized from water to afford N-acetyl-D-phenylalanine as white solid. Melting point at about 163.9-165.3°C SOR at about -39.2° (l%in methanol) |
With sodium hydroxide In water at 20℃; | Typical procedure E for N-acetylation of amino acid General procedure: To a solution of appropriate amino acid (500 mg) in water (20 mL) was added 3N NaOH solution (3.0 eq) and acetic anhydride (5.0 eq). The acidity was set to pH 14 using 3N NaOH solution and the mixture was stirred overnight at room temperature. Then drop the acidity level of the mixture to pH 1 by 3N HCl solution. The reaction mixture was partitioned between chloroform and water. The organic layer was collected, dried over MgSO4 and concentrated under reduced pressure. Methanol added to the residue then was evaporated, and this procedure was conducted several times to remove residual acetic acid. The resulting colorless oil was kept overnight at -18 and it allowed the crystallization of product compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; dicyclohexyl-carbodiimide In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With alpha cyclodextrin In water; acetonitrile pH 7.86; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium phosphate buffer 1.) bio-imprinted α-chymotrypsin, 0 deg C, 30 min, 2.) 1-propanol, -20 deg C, 30 min; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In methanol at 25℃; for 4h; enantioselectivity of reaction dependent on various rhodium complexes with 1,2-bis(phosphanyl)pyrrolidine ligands; various conditions; also N-acetylcinnamic acid methylester; | ||
With 2S-MeN(PPh2)CHC7H7CH2OPPh2; hydrogen other reagents; | ||
With hydrogen In ethanol at 20℃; asymmetric catalytic hydrogenation, enantiodifferentiating ability of the catalysts: atmospheric pressure of H2; var. catalysts, pressure, temp. and initial rate; |
With (+)-(R)-N,N-dimethyl-2-(methylphenylphosphino)aniline; hydrogen; triethylamine In ethanol at 50℃; further co-catalysts: various optically active tertiary dialkylarylphosphines, alkyldiarylphosohines, triarylphosphines and similar arsines; asymmetric induction; | ||
With hydrogen In tetrahydrofuran; triethylamine at 20℃; for 240h; further solvents, further pressure, further reaction times, different mol ratio of ligand/Rh, object of study: optical yield.; | ||
With hydrogen In ethanol; benzene at 20℃; for 0.333333h; var. chiral diphosphinites, var. times, addition of triethylamine in some cases; | ||
With hydrogen In methanol at 22℃; various substrate/catalyst molar ratio; modifications of the catalyst; | ||
With hydrogen In tetrahydrofuran; methanol at 25℃; for 8h; further catalyst: 2,3-bis(dimenthylphosphino)maleic anhydride; reactions under var. conditions; | ||
With hydrogen In tetrahydrofuran; triethylamine at 20℃; for 240h; Title compound not separated from byproducts; | ||
With hydrogen In tetrahydrofuran; methanol at 25℃; for 8h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In tetrahydrofuran; methanol at 25℃; for 8h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In ethanol for 22h; Ambient temperature; Yield given; | ||
With hydrogen In ethanol at 20℃; Title compound not separated from byproducts; | ||
With hydrogen In methanol at 22℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In methanol; benzene at 20℃; | ||
With hydrogen In methanol; benzene at 20℃; for 24h; | ||
66 % ee | With hydrogen In methanol at 40℃; for 15h; | 12 Example 12:7V~-Acetyl-L-phenylalanine; In a 15 mL autoclave in an argon atmosphere bis(benzene)dichlor-ruthenium (2.6 mg,0.005 mmol), (-)-ligand Ib (3.2 mg, 0.006 mmol) and 2-(JV-acetylamino)-cinnamic acid(0.53 g, 2.5 mmol) is dissolved in degassed methanol (5 mL). After flushing the autoclavewith argon hydrogenation is carried out during 15 h at 40 °C and at 50 bar hydrogenpressure. After cooling to room temperature the reaction solution is evaporated and theresidue analysed by HPLC for conversion (column: Bischoff Kromasil 100 C8) and enan-tiomeric excess (column: Nucleodex Beta-PM). Conversion is 34% at an ee of 66%. |
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; C48H42Fe2O2; hydrogen In methanol at 20℃; for 24h; optical yield given as %ee; | ||
43 % ee | With hydrogen In methanol at 40℃; for 16h; | 17 Example 17: ,/V-Acetyl-D-phenylalanine; In a 15 mL autoclave in an argon atmosphere bis(benzene)dichlor-ruthenium (2.6 mg,0.005 mmol), (+)-ligand la (6.0 mg, 0.011 mmol) and Af-acetylaminocinnamic acid (0.53 g,2.5 mmol) is dissolved in degassed methanol (5 mL). After flushing the autoclave withargon hydrogenation is carried out during 16 h at 40 °C and at 50 bar hydrogen pressure.After cooling to room temperature the reaction solution is evaporated and the residueanalysed by HPLC for conversion (column: Bischoff Kromasil 100 C8) and enantiomericexcess (column: Nucleodex Beta-PM). Conversion is 100% at an ee of 43%. |
66 % ee | With hydrogen In methanol at 40℃; for 15h; | 18 Example 18: ./V-Acetyl-L-phenylalaiune; In a 15 mL autoclave in an argon atmosphere bis(benzene)dichlor-ruthenium (2.6 mg,0.005 mmol), (-)-ligand Ib (3.2 mg, 0.006 mmol) and 2-(A/-acetylamino)-cinnamic acid(0.53 g, 2.5 mmol) is dissolved in degassed methanol (5 mL). After flushing the autoclavewith argon hydrogenation is carried out during 15 h at 40 °C and at 50 bar hydrogenpressure. After cooling to room temperature the reaction solution is evaporated and theresidue analysed by HPLC for conversion (column: Bischoff Kromasil 100 C8) andenantiomeric excess (column: Nucleodex Beta-PM). Conversion is 34% at an ee of 66%. |
With 5% Pd(II)/C(eggshell); Cinchonidin In 1,4-dioxane; water at 22.84℃; optical yield given as %ee; enantioselective reaction; | ||
With 5% Pd(II)/C(eggshell); Cinchonin In 1,4-dioxane; water at 22.84℃; optical yield given as %ee; enantioselective reaction; | ||
With hydrogen enantioselective reaction; | ||
With [Rh(α-CgPH)2(cod)]BF4 In methanol at 20℃; for 1h; optical yield given as %ee; enantioselective reaction; | ||
With bis(norbornadiene)rhodium(l)tetrafluoroborate; C24H40FeOP2; hydrogen In ethanol at 20℃; for 2h; enantioselective reaction; | ||
With sodium tetrafluoroborate; chloro(1,5-cyclooctadiene)rhodium(I) dimer; (1S,4R)-3-diphenylphosphino-4-diphenylphosphoryl-cyclohex-2-enyloxy(tert-butyl)diphenylsilane; hydrogen In methanol at 50℃; for 10h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | ||
With BF4(1-)*C40H48O2P2Rh(1+); hydrogen In dichloromethane at 20℃; for 1h; Autoclave; optical yield given as %ee; enantioselective reaction; | 4.4. General procedure for the asymmetric CC-hydrogenation General procedure: A 10 mL stainless steel autoclave equipped with a glass inlet and a magnetic stirring bar was charged under an argon atmosphere with the substrate (1.5 mmol). The desired Rh complex (1.5 μmol) was added by syringe as a stock solution in CH2Cl2 or MeOH. The total amount of solvent was adjusted to 2 mL by the addition of the appropriate quantity of the same solvent and the autoclave was pressurised with hydrogen. The reaction mixture was stirred at room temperature for the desired reaction time (see Table 3 and Table 4) and then the pressure was carefully released. The conversion was determined by 1H NMR spectroscopy of the concentrated reaction mixture. The ee value was determined by chiral GC or HPLC analysis after filtration through a plug of silica. The absolute configurations of the hydrogenation products were assigned by comparison of the sign of the specific rotation with those reported in the literature. | |
With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; (3R, 3aR, 6S, 6aS)-6-(diphenylphosphino)-hexahydrofuro[3,2-b]furan-3-ol; hydrogen In methanol at 20℃; optical yield given as %ee; enantioselective reaction; | ||
52 % ee | With C18H16F6N2O4Pd; hydrogen; benzylamine In 2,2,2-trifluoroethanol at 20℃; Overall yield = 55 %; chemoselective reaction; | α-Acetamidocinnamic and itaconic acids (C=Chydrogenation) General procedure: The corresponding Pd complex (0.05 mmol) was dissolved inthe reactor with the proper amount of MeOH or TFE. The prochiralsubstrate (10 mmol), IA or AA, was then added to the reactor. Insome cases BA (0.05 mmol) was used as an additive. Finally, thereactor was flushed 5 times with pure H2 before setting the pressureto 100 psi. Samples (0.15 mL) were drawn from the reactor to followthe reaction as a function of time. |
79.3 % ee | With {RuCl(C6H6)((S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)}Cl; hydrogen In methanol at 20 - 50℃; for 12h; Autoclave; Inert atmosphere; Overall yield = 83.3 %; enantioselective reaction; | |
With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; carbon monoxide; C56H38O4P2; hydrogen In toluene at 50℃; for 20h; Autoclave; enantioselective reaction; | ||
82 % ee | With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen In tetrahydrofuran at 25℃; for 16h; Autoclave; enantioselective reaction; | |
93 % ee | With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen; (2S,4S)-2,4-bis(diphenylphosphino)pentane In tetrahydrofuran at 25℃; for 16h; Autoclave; enantioselective reaction; | |
67 % ee | With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; 1-(3-(phenyl(o-tolyl)phosphanyl)phenyl)urea; hydrogen In methanol; ethanol at 20℃; for 5h; Inert atmosphere; Autoclave; | |
86 % ee | With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen In tetrahydrofuran at 25℃; for 16h; Inert atmosphere; Autoclave; enantioselective reaction; | |
87 % ee | With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen In tetrahydrofuran at 25℃; for 16h; Inert atmosphere; Autoclave; enantioselective reaction; | |
85 % ee | With hydrogen In methanol at 20℃; for 24h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With hydrogen; triethylamine In methanol at 40℃; for 22h; | 23 Example 23 Preparation of Optically Active N-Acetylphenylalanine Using Rhodium metal complex catalyst The atmosphere in a 25 mL-recovery flask was substituted with nitrogen, and 3 mL of deoxygenized methanol and triethylamine (20.9 μL, 0.15 mmol) were added to the flask as the reaction solvent. α-Acetamidocinnamic acid (0.20 g, 0.98 mmol) and [Rh(CLPL-S)(COD)]BF4 (3.95 mg, 0.0049 mmol) were weighed in a 50 mL-Pyrex (registered trade name) test tube for autoclaving, the tube was put into an autoclave together with a stirrer in the tube, and the atmosphere in the autoclave was substituted with nitrogen. The reaction solvent in a volume of 2 mL was added to the mixture, the atmosphere in the autoclave was sufficiently substituted with hydrogen, and then pressurized with 2 MPa of hydrogen, and the reaction mixture was stirred at 40° C. for 22 hours. After 22 hours, the atmosphere in the autoclave was returned to ordinary pressure, and the reaction mixture was concentrated in an evaporator. The concentrated residue was added with 5 mL of 2 M aqueous sodium hydroxide for dissolution, and the solution was washed with 5 mL of ethyl acetate. The aqueous layer was separated, and added with diluted hydrochloric acid until pH of the aqueous layer became lower than 2, and the produced oil was extracted with 10 mL of ethyl acetate. The organic layer was concentrated in an evaporator to obtain (R)-N-acetylphenylalanine quantitatively. 1H NMR (300 MHz, CD3OD): δ 7.25-7.12 (m, 5H), 4.58 (dd, J=4.8, 8.9 Hz, 1H), 3.15 (dd, J=5.1, 13.8 Hz, 1H), 2.89 (dd, J=9.0, 13.8 Hz, 1H), 1.89 (s, 3H) |
98% | In ethanol | Synthesis No. 9 Synthesis No. 9 0.005 m-mole of rhodium-dinorbornadieneperchlorate, 0.0065 m-mole of (2S,4S)-N-tert.-butoxycarbonyl-2-bis(3,5-dimethyl-4-methoxyphenyl)phosphinomethyl-4-bis(3,5-dimethyl-4-methoxyphenyl)phosphinopyrrolidine (Ii) and 0.25 m-mole of triethylamine were dissolved in 20 ml of ethanol and 5 m-mol of α-acetamidocinnamic acid was added to the solution. The mixture was stirred for 20 hours at 50° C. and under a hydrogen pressure of 20 atm. The reaction mixture was concentrated under reduced pressure and then dissolved in 0.5N aqueous solution of caustic soda. Insolubles were filtered off and the filtrate was made acid with diluted hydrochloric acid and extracted with ether. The organic layer was washed with water and dried. The solvent was distilled off to obtain optically active (R)-N-acetylphenylalanine. Conversion 100%; optical yield 98%. |
96% | With hydrogen In methanol at 30℃; |
96% | With bis(acetonitrile)(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen In methanol at 20℃; for 2h; optical yield given as %ee; enantioselective reaction; | |
95% | With C24H40CoP2; hydrogen; triethylamine; zinc In methanol at 50℃; for 16h; enantioselective reaction; | |
88% | With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen; C38H35NO2P2 In methanol at 25℃; for 12h; Autoclave; High pressure; | |
84.4% | With hydrogen In methanol | 12 (R)-N-Acetylphenylalanine EXAMPLE 12 (R)-N-Acetylphenylalanine A solution of α-acetamido-cinnamic acid (0.5 g, 2.44 mmol) and the catalyst (1) (16 mg, 0.024 mmol, 1.0 mol %) in degassed methanol (10 ml) was placed in a 50 ml Parr pressure reactor purged with nitrogen. The vessel was then purged with hydrogen (*3) and charged to 4.34 MPa (630 psi) of hydrogen. After stirring for 2 h, the solution was evaporated to give (R)-N-acetylphenylalanine (0.52 g, quantitative yield, 84.4% ee). |
With hydrogen In ethanol at 25℃; for 2h; hydrogen pressure dependency of stereoselectivity, effects of added Et3N; | ||
With Zeol-2b <N-(CH2)3Si(OEt)3-protected L-proline - <RhCl(cod)>2 - complex anchored on USY-zeolite); hydrogen at 65℃; for 10h; other α-acylaminocinnamate deriv.; other catalysts; var. reaction times; | ||
100 % Spectr. | With hydrogen; triethylamine In ethanol at 50℃; for 20h; furhter catalysts, reagent concentrations; | |
With hydrogen In ethanol; benzene at 20℃; other catalyst; | ||
4 % Spectr. | With hydrogen In ethanol at 30℃; for 4.3h; study of the asymmetric hydrogenation of various prochiral substrates with chiral ligands containing rhodium(I) complexes of ferrocenylphosphonium as asymmetric catalysts; | |
With <Rh(1(R),5(R),6(R)-1,6-bis(diphenylphosphinoxy)spiro<4.4>nonane>+; hydrogen In methanol at 25℃; for 0.166667h; enantioselectivity; | ||
With hydrogen In methanol for 4h; Ambient temperature; var. Rh cat. with chiral ligands (ee = 30-78percent); | ||
With <(1R)-(o-tolyl)ethyl-FERRIPHOS>; hydrogen In methanol var. ligands: <(1R)-phenylethyl-FERRIPHOS> or <(1R)(2-naphthyl)ethyl-FERRIPHOS>: var. ee. = 97.3-97.6percent; | ||
With hydrogen; triethylamine In ethanol at 25℃; for 2h; Yield given; | ||
With Zeol-2b <N-(CH2)3-Si(OEt)3 -protected L-proline - <RhCl(cod)>2 - complex anchored on USY-zeolite>; hydrogen at 65℃; for 10h; | ||
With hydrogen In tetrahydrofuran Ambient temperature; Yield given; | ||
100 % Spectr. | With hydrogen; triethylamine In ethanol at 50℃; for 20h; | |
With N,N-dimethyl-(S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine; [RhCl(C6H10)]2; hydrogen In methanol; benzene Ambient temperature; | ||
With hydrogen; triethylamine In ethanol for 45h; Ambient temperature; | ||
With hydrogen In ethanol; benzene at 20℃; Yield given; | ||
With <phenyl 4,6-O-benzylidene-2,3-bis-O-<bis<3,5-(trimethylsilyl)phenyl>phosphino>-β-D-glucopyranoside>Rh(COD)>+SbF6-; hydrogen In tetrahydrofuran Ambient temperature; | ||
With hydrogen In ethanol; acetone at 25℃; for 2h; Yield given; | ||
With hydrogen In methanol at 25℃; for 0.166667h; | ||
With <(1R)-(o-tolyl)ethyl-FERRIPHOS>; hydrogen In methanol | ||
With hydrogen In ethanol at 20 - 23℃; | ||
With 1,2,5,6-di-isopropylidene-3,4-bis(diphenylphosphino)-D-mannitol Rh complex*BF4; hydrogen In acetone at -15℃; for 0.25h; | ||
With (1S,2S)-1,2-Bis{di[3',5'-bis(borneoxymethyl)phenyl].}.; hydrogen In methanol | ||
100 % Chromat. | With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; MeO-PEG-supported (3R,4R)-3,4-bis(Ph2P)pyrrolidine; hydrogen In methanol at 20℃; for 4h; | |
With [rhodium(I)(norborna-2,5-diene)2]SbF6; hydrogen; (1S,1S',2R,2R')-1,1'-di-tert-butyl-(2,2’)-diphospholane In methanol at 20℃; for 12h; | ||
With (((1S,2S)-2-t-butylthio-cyclohexyloxy)PPh2)Rh(COD)SbF6; hydrogen In tetrahydrofuran at 20℃; | ||
With copolymeric macroligand; hydrogen In water at 25℃; for 24h; | ||
With hydrogen In methanol at 20℃; | ||
With (4S)-Ph2P-(2S)-Ph2PCH2-pyrrolidine-1-CO-amine dendrimer; hydrogen In methanol at 25℃; | ||
With hydrogen In ethanol at 20℃; for 1.5h; | ||
100 % Turnov. | With hydrogen In methanol at 20℃; for 1h; | |
With hydrogen In dichloromethane at 20℃; for 3h; | ||
99 % ee | With hydrogen In methanol; dichloromethane at 20℃; for 16h; | 3 General Procedure for Catalytic Asymmetric Hydrogenation with Rh(I) Complexes; In a glove box , the catalyst was made by mixing Rh(COD)2BF4 (100 µl of 0.02M solution in CH2Cl2, 2 µmol) and ligand (110 µl of 0,02M solution in CH2Cl2, 2.2 µmol) solutions in the 1.5 ml vial with stirring bar. The mixture was stirred for 15 min and substrate (0.5 ml of 0.4M solution, 0.2 mmol) solution in the appropriate solvent was added. Hydrogenation was performed at room temperature under 8 bar of hydrogen pressure for 16 h. The hydrogen was released and the reaction mixture was passed through a silica gel plug. The conversion and enantiomeric excess was determined by GC or HPLC analysis using a chiral columns without further purification. |
98 % ee | With hydrogen In dichloromethane at 20℃; for 16h; | 3 General Procedure for Catalytic Asymmetric Hydrogenation with Rh(I) Complexes; In a glove box , the catalyst was made by mixing Rh(COD)2BF4 (100 µl of 0.02M solution in CH2Cl2, 2 µmol) and ligand (110 µl of 0,02M solution in CH2Cl2, 2.2 µmol) solutions in the 1.5 ml vial with stirring bar. The mixture was stirred for 15 min and substrate (0.5 ml of 0.4M solution, 0.2 mmol) solution in the appropriate solvent was added. Hydrogenation was performed at room temperature under 8 bar of hydrogen pressure for 16 h. The hydrogen was released and the reaction mixture was passed through a silica gel plug. The conversion and enantiomeric excess was determined by GC or HPLC analysis using a chiral columns without further purification. |
96 % ee | With hydrogen In methanol; dichloromethane at 20℃; for 16h; | 3 General Procedure for Catalytic Asymmetric Hydrogenation with Rh(I) Complexes; In a glove box , the catalyst was made by mixing Rh(COD)2BF4 (100 µl of 0.02M solution in CH2Cl2, 2 µmol) and ligand (110 µl of 0,02M solution in CH2Cl2, 2.2 µmol) solutions in the 1.5 ml vial with stirring bar. The mixture was stirred for 15 min and substrate (0.5 ml of 0.4M solution, 0.2 mmol) solution in the appropriate solvent was added. Hydrogenation was performed at room temperature under 8 bar of hydrogen pressure for 16 h. The hydrogen was released and the reaction mixture was passed through a silica gel plug. The conversion and enantiomeric excess was determined by GC or HPLC analysis using a chiral columns without further purification. |
96 % ee | With hydrogen In dichloromethane at 20℃; for 16h; | 3 General Procedure for Catalytic Asymmetric Hydrogenation with Rh(I) Complexes; In a glove box , the catalyst was made by mixing Rh(COD)2BF4 (100 µl of 0.02M solution in CH2Cl2, 2 µmol) and ligand (110 µl of 0,02M solution in CH2Cl2, 2.2 µmol) solutions in the 1.5 ml vial with stirring bar. The mixture was stirred for 15 min and substrate (0.5 ml of 0.4M solution, 0.2 mmol) solution in the appropriate solvent was added. Hydrogenation was performed at room temperature under 8 bar of hydrogen pressure for 16 h. The hydrogen was released and the reaction mixture was passed through a silica gel plug. The conversion and enantiomeric excess was determined by GC or HPLC analysis using a chiral columns without further purification. |
94 % ee | With hydrogen In methanol; dichloromethane at 20℃; for 16h; | 3 General Procedure for Catalytic Asymmetric Hydrogenation with Rh(I) Complexes; In a glove box , the catalyst was made by mixing Rh(COD)2BF4 (100 µl of 0.02M solution in CH2Cl2, 2 µmol) and ligand (110 µl of 0,02M solution in CH2Cl2, 2.2 µmol) solutions in the 1.5 ml vial with stirring bar. The mixture was stirred for 15 min and substrate (0.5 ml of 0.4M solution, 0.2 mmol) solution in the appropriate solvent was added. Hydrogenation was performed at room temperature under 8 bar of hydrogen pressure for 16 h. The hydrogen was released and the reaction mixture was passed through a silica gel plug. The conversion and enantiomeric excess was determined by GC or HPLC analysis using a chiral columns without further purification. |
99 % ee | With hydrogen In dichloromethane at 20℃; for 16h; | 3 General Procedure for Catalytic Asymmetric Hydrogenation with Rh(I) Complexes; In a glove box , the catalyst was made by mixing Rh(COD)2BF4 (100 µl of 0.02M solution in CH2Cl2, 2 µmol) and ligand (110 µl of 0,02M solution in CH2Cl2, 2.2 µmol) solutions in the 1.5 ml vial with stirring bar. The mixture was stirred for 15 min and substrate (0.5 ml of 0.4M solution, 0.2 mmol) solution in the appropriate solvent was added. Hydrogenation was performed at room temperature under 8 bar of hydrogen pressure for 16 h. The hydrogen was released and the reaction mixture was passed through a silica gel plug. The conversion and enantiomeric excess was determined by GC or HPLC analysis using a chiral columns without further purification. |
In ethanol; triethylamine | Synthesis: Nos. 1-5 Synthesis: Nos. 1-5 0.0025 m-mol of rhodium-1,5-cyclooctadienechloride complex, 0.0065 m-mol of one of the asymmetric ligand compounds indicated in Table 1 and 0.25 m-mol of triethylamine were dissolved in 20 ml of ethanol, and 5 m-mol of α-acetamidocinnamic acid was added to the solution. The mixture was stirred for 20 hours at 50° C. and under a hydrogen atmosphere of 20 atm. The reaction mixture was concentrated under reduced pressure and then dissolved in 0.5N aqueous solution of caustic soda. Insolubles were filtered off and the filtrate was made acid with diluted hydrochloric acid and extracted with ether. The organic layer was washed with water and dried. The solvent was distilled off to obtain optically active (R)-N-acetylphenylalanine. The results of Synthesis Nos. 1-5 are shown in Table 1. | |
99.5 % ee | With hydrogen In methanol at 30℃; for 0.416667h; | |
With hydrogen In methanol; toluene at 20℃; for 2h; | ||
With hydrogen In methanol at 20℃; for 0.1h; | ||
With hydrogen In methanol at 30℃; for 0.416667h; | ||
With hydrogen; triethylamine In methanol at 40℃; for 22h; | 24 Examples 24 to 28Preparation of Optically Active N-Acetylphenylalanine Using Rhodium Metal Complex CatalystThe target compounds were synthesized in the same manner as that of Example 23 except for the metal complex catalyst.; Example 23 Preparation of Optically Active N-Acetylphenylalanine Using Rhodium metal complex catalyst The atmosphere in a 25 mL-recovery flask was substituted with nitrogen, and 3 mL of deoxygenized methanol and triethylamine (20.9 μL, 0.15 mmol) were added to the flask as the reaction solvent. α-Acetamidocinnamic acid (0.20 g, 0.98 mmol) and [Rh(CLPL-S)(COD)]BF4 (3.95 mg, 0.0049 mmol) were weighed in a 50 mL-Pyrex (registered trade name) test tube for autoclaving, the tube was put into an autoclave together with a stirrer in the tube, and the atmosphere in the autoclave was substituted with nitrogen. The reaction solvent in a volume of 2 mL was added to the mixture, the atmosphere in the autoclave was sufficiently substituted with hydrogen, and then pressurized with 2 MPa of hydrogen, and the reaction mixture was stirred at 40° C. for 22 hours. After 22 hours, the atmosphere in the autoclave was returned to ordinary pressure, and the reaction mixture was concentrated in an evaporator. The concentrated residue was added with 5 mL of 2 M aqueous sodium hydroxide for dissolution, and the solution was washed with 5 mL of ethyl acetate. The aqueous layer was separated, and added with diluted hydrochloric acid until pH of the aqueous layer became lower than 2, and the produced oil was extracted with 10 mL of ethyl acetate. The organic layer was concentrated in an evaporator to obtain (R)-N-acetylphenylalanine quantitatively. 1H NMR (300 MHz, CD3OD): δ 7.25-7.12 (m, 5H), 4.58 (dd, J=4.8, 8.9 Hz, 1H), 3.15 (dd, J=5.1, 13.8 Hz, 1H), 2.89 (dd, J=9.0, 13.8 Hz, 1H), 1.89 (s, 3H) | |
With hydrogen; triethylamine In methanol at 40℃; for 22h; | 25 Examples 24 to 28Preparation of Optically Active N-Acetylphenylalanine Using Rhodium Metal Complex CatalystThe target compounds were synthesized in the same manner as that of Example 23 except for the metal complex catalyst.; Example 23 Preparation of Optically Active N-Acetylphenylalanine Using Rhodium metal complex catalyst The atmosphere in a 25 mL-recovery flask was substituted with nitrogen, and 3 mL of deoxygenized methanol and triethylamine (20.9 μL, 0.15 mmol) were added to the flask as the reaction solvent. α-Acetamidocinnamic acid (0.20 g, 0.98 mmol) and [Rh(CLPL-S)(COD)]BF4 (3.95 mg, 0.0049 mmol) were weighed in a 50 mL-Pyrex (registered trade name) test tube for autoclaving, the tube was put into an autoclave together with a stirrer in the tube, and the atmosphere in the autoclave was substituted with nitrogen. The reaction solvent in a volume of 2 mL was added to the mixture, the atmosphere in the autoclave was sufficiently substituted with hydrogen, and then pressurized with 2 MPa of hydrogen, and the reaction mixture was stirred at 40° C. for 22 hours. After 22 hours, the atmosphere in the autoclave was returned to ordinary pressure, and the reaction mixture was concentrated in an evaporator. The concentrated residue was added with 5 mL of 2 M aqueous sodium hydroxide for dissolution, and the solution was washed with 5 mL of ethyl acetate. The aqueous layer was separated, and added with diluted hydrochloric acid until pH of the aqueous layer became lower than 2, and the produced oil was extracted with 10 mL of ethyl acetate. The organic layer was concentrated in an evaporator to obtain (R)-N-acetylphenylalanine quantitatively. 1H NMR (300 MHz, CD3OD): δ 7.25-7.12 (m, 5H), 4.58 (dd, J=4.8, 8.9 Hz, 1H), 3.15 (dd, J=5.1, 13.8 Hz, 1H), 2.89 (dd, J=9.0, 13.8 Hz, 1H), 1.89 (s, 3H) | |
With hydrogen; triethylamine In methanol at 40℃; for 22h; | 26 Examples 24 to 28Preparation of Optically Active N-Acetylphenylalanine Using Rhodium Metal Complex CatalystThe target compounds were synthesized in the same manner as that of Example 23 except for the metal complex catalyst.; Example 23 Preparation of Optically Active N-Acetylphenylalanine Using Rhodium metal complex catalyst The atmosphere in a 25 mL-recovery flask was substituted with nitrogen, and 3 mL of deoxygenized methanol and triethylamine (20.9 μL, 0.15 mmol) were added to the flask as the reaction solvent. α-Acetamidocinnamic acid (0.20 g, 0.98 mmol) and [Rh(CLPL-S)(COD)]BF4 (3.95 mg, 0.0049 mmol) were weighed in a 50 mL-Pyrex (registered trade name) test tube for autoclaving, the tube was put into an autoclave together with a stirrer in the tube, and the atmosphere in the autoclave was substituted with nitrogen. The reaction solvent in a volume of 2 mL was added to the mixture, the atmosphere in the autoclave was sufficiently substituted with hydrogen, and then pressurized with 2 MPa of hydrogen, and the reaction mixture was stirred at 40° C. for 22 hours. After 22 hours, the atmosphere in the autoclave was returned to ordinary pressure, and the reaction mixture was concentrated in an evaporator. The concentrated residue was added with 5 mL of 2 M aqueous sodium hydroxide for dissolution, and the solution was washed with 5 mL of ethyl acetate. The aqueous layer was separated, and added with diluted hydrochloric acid until pH of the aqueous layer became lower than 2, and the produced oil was extracted with 10 mL of ethyl acetate. The organic layer was concentrated in an evaporator to obtain (R)-N-acetylphenylalanine quantitatively. 1H NMR (300 MHz, CD3OD): δ 7.25-7.12 (m, 5H), 4.58 (dd, J=4.8, 8.9 Hz, 1H), 3.15 (dd, J=5.1, 13.8 Hz, 1H), 2.89 (dd, J=9.0, 13.8 Hz, 1H), 1.89 (s, 3H) | |
With hydrogen; triethylamine In methanol at 40℃; for 22h; | 27 Examples 24 to 28Preparation of Optically Active N-Acetylphenylalanine Using Rhodium Metal Complex CatalystThe target compounds were synthesized in the same manner as that of Example 23 except for the metal complex catalyst.; Example 23 Preparation of Optically Active N-Acetylphenylalanine Using Rhodium metal complex catalyst The atmosphere in a 25 mL-recovery flask was substituted with nitrogen, and 3 mL of deoxygenized methanol and triethylamine (20.9 μL, 0.15 mmol) were added to the flask as the reaction solvent. α-Acetamidocinnamic acid (0.20 g, 0.98 mmol) and [Rh(CLPL-S)(COD)]BF4 (3.95 mg, 0.0049 mmol) were weighed in a 50 mL-Pyrex (registered trade name) test tube for autoclaving, the tube was put into an autoclave together with a stirrer in the tube, and the atmosphere in the autoclave was substituted with nitrogen. The reaction solvent in a volume of 2 mL was added to the mixture, the atmosphere in the autoclave was sufficiently substituted with hydrogen, and then pressurized with 2 MPa of hydrogen, and the reaction mixture was stirred at 40° C. for 22 hours. After 22 hours, the atmosphere in the autoclave was returned to ordinary pressure, and the reaction mixture was concentrated in an evaporator. The concentrated residue was added with 5 mL of 2 M aqueous sodium hydroxide for dissolution, and the solution was washed with 5 mL of ethyl acetate. The aqueous layer was separated, and added with diluted hydrochloric acid until pH of the aqueous layer became lower than 2, and the produced oil was extracted with 10 mL of ethyl acetate. The organic layer was concentrated in an evaporator to obtain (R)-N-acetylphenylalanine quantitatively. 1H NMR (300 MHz, CD3OD): δ 7.25-7.12 (m, 5H), 4.58 (dd, J=4.8, 8.9 Hz, 1H), 3.15 (dd, J=5.1, 13.8 Hz, 1H), 2.89 (dd, J=9.0, 13.8 Hz, 1H), 1.89 (s, 3H) | |
With hydrogen; triethylamine In methanol at 40℃; for 22h; | 28 Examples 24 to 28Preparation of Optically Active N-Acetylphenylalanine Using Rhodium Metal Complex CatalystThe target compounds were synthesized in the same manner as that of Example 23 except for the metal complex catalyst.; Example 23 Preparation of Optically Active N-Acetylphenylalanine Using Rhodium metal complex catalyst The atmosphere in a 25 mL-recovery flask was substituted with nitrogen, and 3 mL of deoxygenized methanol and triethylamine (20.9 μL, 0.15 mmol) were added to the flask as the reaction solvent. α-Acetamidocinnamic acid (0.20 g, 0.98 mmol) and [Rh(CLPL-S)(COD)]BF4 (3.95 mg, 0.0049 mmol) were weighed in a 50 mL-Pyrex (registered trade name) test tube for autoclaving, the tube was put into an autoclave together with a stirrer in the tube, and the atmosphere in the autoclave was substituted with nitrogen. The reaction solvent in a volume of 2 mL was added to the mixture, the atmosphere in the autoclave was sufficiently substituted with hydrogen, and then pressurized with 2 MPa of hydrogen, and the reaction mixture was stirred at 40° C. for 22 hours. After 22 hours, the atmosphere in the autoclave was returned to ordinary pressure, and the reaction mixture was concentrated in an evaporator. The concentrated residue was added with 5 mL of 2 M aqueous sodium hydroxide for dissolution, and the solution was washed with 5 mL of ethyl acetate. The aqueous layer was separated, and added with diluted hydrochloric acid until pH of the aqueous layer became lower than 2, and the produced oil was extracted with 10 mL of ethyl acetate. The organic layer was concentrated in an evaporator to obtain (R)-N-acetylphenylalanine quantitatively. 1H NMR (300 MHz, CD3OD): δ 7.25-7.12 (m, 5H), 4.58 (dd, J=4.8, 8.9 Hz, 1H), 3.15 (dd, J=5.1, 13.8 Hz, 1H), 2.89 (dd, J=9.0, 13.8 Hz, 1H), 1.89 (s, 3H) | |
87 % ee | With hydrogen In methanol at 40℃; for 22h; | 29 Examples 29 to 30; Preparation of Optically Active N-Acetylphenylalanine Using Rhodium Metal Complex Catalystα-Acetamidocinnamic acid (0.20 g, 0.98 mmol), [RhCl(COD)]2 (1.2 mg, 0.0025 mmol) and a ligand (0.005 mmol) were weighed in a 50 mL-Pyrex (registered trade name) test tube for autoclaving, and a stirrer was put into the tube. This test tube was set in a 50 mL-autoclave, and the atmosphere in the autoclave was substituted three times with nitrogen. The reaction mixture was added with 2 mL of degassed methanol, the atmosphere in the autoclave was sufficiently substituted with hydrogen, and then pressurized with 0.8 MPa of hydrogen, and the reaction mixture was stirred at 40° C. for 22 hours. The post-treatment after the reaction was performed in the same manner as that of Example 23. |
94 % ee | With 6-((1R,2S)-1-(diphenylphosphino)-3-methoxy-1-phenylprop-2-yloxy)dibenzo[d,f][1,3,2]dioxaphosphepine; hydrogen In tetrahydrofuran at -40℃; | 11 Example 11. Asymmetric hydrogenation of different unsaturated hydrocarbon compounds with chiral ligand 2 and [Rh(nbd)2]BF4 at -40 0CThe following compounds (a-n) were hydrogenated in presence of a catalyst of the invention (ligand 2 and [Rh(nbd)2]BF4) at -40 0C. |
99 % ee | With (11bP)-4-((1R,2S)-1-(diphenylphosphino)-3-methoxy-1-phenylprop-2-yloxy)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine; hydrogen In tetrahydrofuran at 20℃; | 12 Example 12. Asymmetric hydrogenation of different unsaturated hydrocarbon compounds with chiral ligand 6 and [Rh(nbd)2]BF4 at room temperature.The following compounds were hydrogenated in presence of a catalyst of the invention (ligand 6 and [Rh(nbd)2]BF4) at room temperature. |
With Rh[(nbd)((2S,2'S,3S,3'S)-BIBOP)]BF4; hydrogen In methanol at 0℃; for 12h; Autoclave; optical yield given as %ee; enantioselective reaction; | ||
With (R,R)-2,3-bis(tert-butylmethylphosphino)quinoxaline(1,5-cyclooctadiene)rhodium(I) hexafluoroantimonate; hydrogen In methanol at 20℃; for 0.2h; optical yield given as %ee; | ||
93 % ee | With BF4(1-)*C40H42NO2P3Rh(1+); hydrogen In methanol at 20℃; for 3h; Autoclave; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 89% 2: 11% | With [Rh(cod)(Xylophos)](1+)*BF4(1-); hydrogen In methanol at 19.85℃; for 6h; | |
With hydrogen In methanol; water at 50℃; other rhodium(I)-complexes, various reaction conditions: time, pressure and temperatures; other derivatives of acetamidoacryl acid; | ||
With hydrogen In methanol at 20 - 30℃; for 72h; various di- and triphosphines, other temperatures and times; |
With hydrogen various temp., pressure, catalysts, solvents and amines; | ||
With hydrogen In tetrahydrofuran for 1h; Ambient temperature; different chiral catalysts; | ||
With hydrogen; triethylamine In ethanol at 20℃; other catalysts; | ||
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (R)-1-[(S)-1',2-bis(diphenylphosphino)ferrocenyl]ethanol; hydrogen In methanol at 50℃; for 48h; | ||
With rhodium-diene complex with (S,S)-2,4-bis(bis(p-N,N-dimethylaminophenyl)phosphino)pentane; hydrogen In methanol at 25℃; other chiral ligands, solvents, temp., and pressure; var. dehydroamino acids; | ||
With 6S-cyano-5R-diphenylphosphino-3R,4S-O-isopropylidene-2-oxa-bicyclo<3.2.0>heptane Rh; hydrogen In methanol; benzene for 72h; Ambient temperature; variation of time and pressure; | ||
With 6S-aminomethyl-5R-diphenylphosphino-3R,4S-O-isopropylidene-2-oxa-bicyclo<3.2.0>heptane Rh-; hydrogen In methanol; benzene for 72h; Ambient temperature; variation of time and pressure; | ||
With hydrogen In ethanol; water at 80℃; for 4h; other chiral rhodium(I) complexes, effect of H2 pressure, temperature, substrate concentration; | ||
With formic acid; triethylamine In dimethyl sulfoxide at 45℃; different catalysts, temperatures, solvents; | ||
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; 3α-diphenylphosphino-2α-(2'-diphenylphosphinoethyl)-5α-cholestane; hydrogen In ethanol; benzene Ambient temperature; chiral diphosphine ligands in metal-catalysed asymetric synthesis; other chiral diphosphine ligands, other unsaturated compounds, other reaction partners; | ||
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; hydrogen; (2R,3R)-2,3-diphenyl-1,4-bis(diphenylphosphino)butane In methanol at 25℃; other α-aminoacid derivatives, var. optically active 1,4-bis(diphenylphosphino)butane derivatives; | ||
With hydrogen In methanol; toluene for 72h; Ambient temperature; other pressure, other time; other 2-(acetamido)acrylic acids; | ||
With <Rh(Ph-β-glup)(COD)>BF4; bisphosphinite; hydrogen In methanol at 25℃; various rhodiun(I)-chelates and solvents; | ||
With (<i>S</i>)-1-phenyl-ethylamine; hydrogen In 1,2-dimethoxyethane for 12h; other solvents, reagents ratio; | ||
With Rh(I) di-1,5-cyclooctadiene complex with (R,R)-1,2-bis<N-methyl(diphenylphosphino)amino>cyclohexane; hydrogen In ethanol Ambient temperature; other α-acylaminoacrylic acids, other chiral Rh(I) aminophosphine complexes; | ||
With hydrogen; triethylamine In ethanol for 45h; Ambient temperature; various (Z)-2-acetamidoacrylic acid derivatives, pressures, times, temperatures; | ||
With <Rh(R-PheNOP)(COD)>ClO4; hydrogen optical yield; | ||
With (4R,5R)-<(2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)>bis(3,5-dimethyl-4-methoxyphenyl)rhodium(I) tetrafluoroborate (Rh+-DIOP (7)); hydrogen In ethanol at 50℃; for 4h; var. modified DIOP complexes of Rh(I) and Rh(0); also (Z)-N-(1-phenylpropenyl)acetamide; | ||
With hydrogen In methanol percent ee, different temperature and different ratio of reaction partners; | ||
With Rh(1,5-cyclooctadiene)((1S,2S)-1,2-bis(diphenylphosphinamino)cyclohexane)(1+)*ClO4(1-); hydrogen; triethylamine In ethanol; benzene asymmetric homogeneous hydrogenation of olefins with the chiral aminophosphine-rhodium complexes; other olefins; other chiral aminophosphine rhodium complex; var. ratios of reagents; | ||
With Rh(1,5-cyclooctadiene)((2S,3S)-2,3-bis(diphenylphosphinamino)butane)(1+)*ClO4(1-); hydrogen In isopropyl alcohol asymmetric homogeneous hydrogenation of olefins with the chiral aminophosphine-rhodium complexes; other α-acylaminocinnamic acid derivatives; other chiral aminophosphine rhodium complexes; var. solvents; | ||
With hydrogen In water; ethyl acetate different pressure of H2, presence of KPF6, other Rh catalysts; | ||
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,S)-DIOP-boron analog; hydrogen In ethanol at 25℃; for 3h; other unsaturated compounds, other reagents, other solvents, var. pressure, temp. and time; | ||
With (-)-DIOCOL; hydrogen In methanol; benzene at 25℃; for 16h; other α,β-unsaturated acids and esters; | ||
With hydrogen var. chiral Rh complex cat.: determination eepercent : 59.3-80.0percent; | ||
With disodium hydrogenphosphate; hydrogen In water at 25℃; for 24h; further solvent, different catalysts; | ||
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; 3,4-bis-O-(1,3,2-dioxaphospholano)-1,2:5,6-di-O-isopropylidene-D-mannit; hydrogen In ethanol; toluene for 69h; Ambient temperature; further reagents, reaction times, solvents, temperatures, enantioselectivity; | ||
With hydrogen In ethanol Ambient temperature; other substrates, other conditions, enantioselectivity; | ||
With hydrogen; sodium dodecyl-sulfate In water at 25℃; enantioselectivity; half-life; | ||
With hydrogen; rhodium; 1,2-bis(bis-2-<(+)-menthoxycarbonyl>ethyl)phosphanobenzene In methanol hydrogenation with further phosphanes in situ catalysts; | ||
With hydrogen In ethanol; benzene at 24 - 25℃; for 24h; other Rh(I)-BDPAB complexes as catalyst, var. solvents, different H2 pressure; | ||
With <(3R,4R)-N-<1,5-dioxo-5-(TentaGel-N-)pentyl>-3,4-bis(diphenylphosphanyl)pyrrolidine-P,P'>(1,5-cyclooctadiene)rhodium tetrafluoroborate; hydrogen In methanol; benzene at 25℃; for 3.33333h; enantioselectivity, var. of catalyst, solvent, ratio; | ||
With hydrogen In water for 2h; other solvents, times; | ||
With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen; triethylamine; (2R,2'R)-bis(diphenylphosphino)-(1R,1'R)-dicyclopentane In ethanol for 24h; Ambient temperature; other dehydroaminoacid derivatives, other reagent: <Rh(COD)Cl>2, triethylamine absence, other solvents: THF, 1,2-dichloroethane; | ||
With RuCl2<(R)-bis(3-dehydroxy-3-diphenylphosphinoequilenin-4-yl)>(DMF)2; hydrogen for 72h; various catalysts, enantioselectivity; | ||
With hydrogen In methanol; toluene at 25℃; for 20h; various ligands, times, and pressures; | ||
With hydrogen In methanol at 2℃; for 0.166667h; bicyclo<3.2.0>heptan-3-endo,6-endo-diol bis(diphenylphosphinate)*Rh(+)(cod)*CF3SO3(-) as a catalyst; various temp.; | ||
With hydrogen In methanol at 25℃; for 260h; other temp., pressures and reaction times; various catalysts; | ||
With formic acid; sodium formate In water at 90℃; for 12h; asymmetric transfer hydrogenation of acrylic acids catalyzed by Rh(I) complexes of chiral and achiral diphosphine ligands using also formic acid-triethylamine as H source; varying solvent, temperature; | ||
With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; 3,3'-di-O-benzyl-4,6:4',6'-di-O-benzylidene-2,2'-di-O-diphenylphosphino-α,α-trehalose; hydrogen In tetrahydrofuran; ethanol for 24h; Ambient temperature; other reagents 4,6:4',6'-di-O-benzylidene-2,2'-di-O-diphenylpohosphino-3,3'-di-O-methyl-α,α-trehalose; | ||
With formic acid; triethylamine In dimethyl sulfoxide at 45℃; for 20h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With <<(S,S)-2,4-bis<bis(p-N,N-dimethylammoniumphenyl)phosphino>pentane>Rh(η4-bicyclo<2.2.1>hepta-2,5-diene)>*(BF4)5; hydrogen In methanol at 20℃; for 0.085h; | ||
With hydrogen In ethanol at 25℃; Yield given. Yields of byproduct given; | ||
In ethanol; benzene for 48h; Yield given; | ||
With hydrogen; triethylamine In ethanol at 20℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (R)-1-[(S)-1',2-bis(diphenylphosphino)ferrocenyl]ethanol; hydrogen In methanol at 50℃; for 48h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In water at 25℃; for 6h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In ethanol for 48h; Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In ethanol; benzene for 24h; Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen; triethylamine In tetrahydrofuran; ethanol at 35℃; for 24h; RuHCl-bis<(R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl>, with and without Et3N; Title compound not separated from byproducts; | ||
With hydrogen In ethanol at 32℃; for 48h; Yield given; | ||
With hydrogen In ethanol for 48h; Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With tetraethylammonium fluoride In dimethyl sulfoxide at 45℃; for 20h; Yield given. Yields of byproduct given; | ||
With hydrogen In tetrahydrofuran for 6h; Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With |
||
With <(1S;2R-MAC-PONP)Rh(COD)>(+)BF4(-); hydrogen In 1,4-dioxane at 30℃; Title compound not separated from byproducts; | ||
With hydrogen; triethylamine In methanol; benzene at 25℃; Yield given. Yields of byproduct given; | ||
With hydrogen In methanol Ambient temperature; Yield given. Title compound not separated from byproducts; | ||
With hydrogen In water; ethyl acetate at 25℃; Title compound not separated from byproducts; | ||
With hydrogen In tetrahydrofuran; ethanol at 35℃; for 24h; Title compound not separated from byproducts; | ||
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (2R,3R)-2,3-dicyclohexyl-1,4-bis(diphenylphosphino)butane; hydrogen In ethanol at 25℃; Yield given. Title compound not separated from byproducts; | ||
With hydrogen for 0.25h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With (-)-DIOCOL; hydrogen In methanol; benzene at 25℃; for 16h; Yield given. Title compound not separated from byproducts; | ||
With <Ru(BINAP-4SO3Na)Cl2>; hydrogen In water for 48h; Ambient temperature; Title compound not separated from byproducts; | ||
With hydrogen In methanol Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (+)-O,N-bis(diphenylphosphino)-2-exo-hydroxy-3-endo-methylaminonorbornane; hydrogen In methanol at 25℃; Yield given. Yields of byproduct given; | ||
With hydrogen In ethanol at 25℃; for 0.2h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In methanol; benzene for 24h; Ambient temperature; Yield given. Title compound not separated from byproducts; | ||
With Rh complex of (S,S)-1,2-bis<o-ethylphenyl)phenylphosphino>ethane; hydrogen In isopropyl alcohol at 50℃; for 3h; | ||
With <Rh(COD)(R,R)-4,5-bis(diphenylphosphinomethyl)-2-(4'-hydroxyphenyl)-1,3-dioxolane>BF4; hydrogen In methanol at 25℃; for 0.0333333h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In water; ethyl acetate for 0.833333h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In methanol for 12h; Ambient temperature; | ||
With RuCl2<(R)-bis(3-dehydroxy-3-diphenylphosphinoequilenin-4-yl)>(DMF)2; hydrogen for 48h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In methanol at 2℃; for 0.166667h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With formic acid; sodium formate In water at 90℃; for 12h; Yield given. Yields of byproduct given; | ||
With hydrogen; sodium dodecyl-sulfate In water at 25℃; | ||
With hydrogen In methanol for 4h; Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With formic acid; triethylamine In dimethyl sulfoxide at 27℃; for 20h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen; rac-methylbenzylamine In ethanol at 0℃; Yield given. Yields of byproduct given; | ||
With hydrogen; triethylamine In ethanol at 20℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen; triethylamine In ethanol at 20℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In methanol Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In methanol; benzene for 72h; Ambient temperature; Yield given. Further byproducts given; | ||
With hydrogen In ethanol; benzene Ambient temperature; Yield given. Yields of byproduct given; | ||
With hydrogen In methanol at 32℃; for 25h; Yield given; | ||
With hydrogen In ethanol; water at 80℃; for 4h; | ||
With hydrogen In methanol; benzene for 72h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; 3α-diphenylphosphino-2α-(2'-diphenylphosphinoethyl)-5α-cholestane; hydrogen In ethanol; benzene Ambient temperature; Yield given. Title compound not separated from byproducts; | ||
With <Rh(Ph-β-glup)(COD)>BF4; bisphosphinite; hydrogen In methanol at 25℃; Yield given; | ||
With [RhCl(C6H10)]2; (R)-N,N-dimethyl-1-((S)-1',2-bis(diphenylphosphino)ferrocenyl)ethylamine; hydrogen In methanol; benzene Ambient temperature; | ||
With Rh(I) complex with (R,R)-1,2-bis(N-methyl(diphenylphosphino)amino)cyclohexane; hydrogen In ethanol Ambient temperature; Title compound not separated from byproducts; | ||
With <(1R;2R-MAC-PONP)Rh(COD)>(+)BF4(-); hydrogen In isopropyl alcohol at 30℃; Title compound not separated from byproducts; | ||
With ethanol; Rh(1,5-cyclooctadiene)((1S,2S)-1,2-bis(diphenylphosphinamino)cyclohexane)(1+)*ClO4(1-); hydrogen; triethylamine In benzene Title compound not separated from byproducts; | ||
With Rh(1,5-cyclooctadiene)((2S,3S)-2,3-bis(diphenylphosphinamino)butane)(1+)*ClO4(1-); hydrogen; isopropyl alcohol In benzene Title compound not separated from byproducts; | ||
With hydrogen In water; ethyl acetate at 25℃; Title compound not separated from byproducts; | ||
With hydrogen In methanol; toluene for 72h; Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In methanol at 50℃; for 24h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With water In ethanol at 25℃; for 2h; Microbiological reaction; optical yield given as %ee; enantioselective reaction; | |
at 35℃; for 48h; in the present of Saccharomyces cerevisiae Hansen; Yield given. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In methanol at 22℃; various substrate/catalyst molar ratio; modifications of the catalyst; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With lipase AS 'Amano'; at 35℃; for 24h;pH 6.5;Enzymatic reaction;Catalytic behavior; | General procedure: Kinetic resolution of (RS)-2-acetamido-2-phenylacetic acid (Table 2, entry 1). A 25 ml round-bottomed flask was charged with (RS)-2-acetamido-2-phenylacetic acid at a concentration of 50 mM and 5 mL of phosphorus buffer solution at pH 6.5. Next, 4.2 mg of free enzyme powder of lipase AS ?Amano? was added to the mixture. When this was completed, the resulting mixture was stirred at 35 C for 24 h. Yields and ee values of the products were determined by HPLC analysis. When the reaction was completed, the solution was filtered through a pad of cotton. The solution was changed to pH 7.0, extracted with ethyl acetate three times, and the combined organic solution was dried over anhydrous magnesium sulfate and then evacuated to remove the organic solvent. The resulting residues were purified by column chromatography on silica gel with petroleum ether/ethyl acetate (1:10-1:5) to afford the pure amino acids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With benzotriazol-1-ol; dicyclohexyl-carbodiimide In dichloromethane for 18h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With benzotriazol-1-ol; triethylamine; dicyclohexyl-carbodiimide In chloroform |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With benzotriazol-1-ol; triethylamine; dicyclohexyl-carbodiimide Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With benzotriazol-1-ol; dicyclohexyl-carbodiimide In dichloromethane Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With benzotriazol-1-ol; triethylamine; dicyclohexyl-carbodiimide In chloroform |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With benzotriazol-1-ol; triethylamine; dicyclohexyl-carbodiimide In chloroform |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With benzotriazol-1-ol; triethylamine; dicyclohexyl-carbodiimide In chloroform |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With benzotriazol-1-ol; triethylamine; dicyclohexyl-carbodiimide In chloroform |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With sodium tetrahydroborate; iodine In tetrahydrofuran Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | for 36h; carbonate hydrolyase EC 4.2.2.1 (bovine carbonic anhydrase, BCA), pH 7.5; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; triethylamine In tetrahydrofuran; ethanol at 35℃; for 24h; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; triethylamine In tetrahydrofuran; ethanol at 35℃; for 24h; RuHCl-bis<(R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl>, with and without Et3N; Title compound not separated from byproducts; | ||
With hydrogen In ethanol at 20℃; for 0.5h; | ||
With hydrogen In ethanol at 20℃; for 0.5h; |
With hydrogen; triethylamine In methanol for 22h; Ambient temperature; Title compound not separated from byproducts; | ||
With hydrogen In methanol Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With {(1,5-cyclooctadiene)Rh(1,2-bis((2R,5R)-2,5-diethylphospholano)benzene)}triflate; hydrogen In isopropyl alcohol at 20℃; for 24h; Title compound not separated from byproducts; | ||
With (4S,5S)-1,3-dibenzyl-4-[(S)-1-diphenylphosphinoethyl]-5-[(R)-1-diphenylphosphinoethyl]imidazolidin-2-one; hydrogen In acetone at 20℃; for 1h; Title compound not separated from byproducts; | ||
With (4S,5S)-1,3-dibenzyl-4-[(S)-1-diphenylphosphinoethyl]-5-[(R)-1-diphenylphosphinoethyl]imidazolidin-2-one; hydrogen In acetone at 20℃; for 1h; Title compound not separated from byproducts; | ||
With hydrogen; rhodium(1+); (S(P),S(P))-1,2-bis[(o-anisyl)(phenyl)phosphino]ethane In methanol optical yield given as %ee; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; acetonitrile at 25℃; furhter bilayer catalytic systems; kcat; | ||
With Nα-tetradecanoyl-L-histidine In water; acetonitrile at 10℃; ΔH(excit.), ΔS(excit.); Tris-KCl buffer, didodecyldimethylammonium bromide; other nucleophiles and surfactants; other temp.; | ||
With water at 23℃; pH 5.6; different poly(iminomethylene) 1-cetylpyridinium complexes catalysts and pH-s; |
With Z-L-Leu-L-His-L-Leu; Tris buffer; N,N-didodecyl-N,N-dimethylammonium bromide In acetonitrile at 24.9℃; pH: 7.68, μ = 0.15 (KCl); other peptide catalyst; binding constants Kb/N; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pH 7.0 In water at 30℃; further enzymes; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In water at 22℃; for 1h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With hydrogen In water at 60℃; for 92h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With benzotriazol-1-ol; toluene-4-sulfonic acid; dicyclohexyl-carbodiimide In N,N-dimethyl-formamide Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With benzotriazol-1-ol; dicyclohexyl-carbodiimide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With benzotriazol-1-ol; dicyclohexyl-carbodiimide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 4-methyl-morpholine In tetrahydrofuran at -15℃; for 0.0333333h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In methanol at 25℃; for 1h; | ||
43 % ee | With (+)-2,6'-bis(diphenylphosphino)-2'-methoxy-1,1'-biphenyl; hydrogen In methanol at 40℃; for 16h; | 21 In a 15 mL autoclave in an argon atmosphere bis(benzene)dichlor-ruthenium (2.6 mg, 0.005 mmol), (+)-ligand Ia (6.0 mg, 0.011 mmol) and N-acetylaminocinnamic acid (0.53 g, 2.5 mmol) is dissolved in degassed methanol (5 mL). After flushing the autoclave with argon hydrogenation is carried out during 16 h at 40 °C and at 50 bar hydrogen pressure. After cooling to room temperature the reaction solution is evaporated and the residue analysed by HPLC for conversion (column: Bischoff Kromasil 100 C8) and enantiomeric excess (column: Nucleodex b-PM). Conversion is 100% at an ee of 43%. |
With bis(norbornadiene)rhodium(l)tetrafluoroborate; (11bM)-4-((1R,2S)-1-(diphenylphosphino)-3-methoxy-1-phenylprop-2-yloxy)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine; hydrogen In tetrahydrofuran at 20℃; for 12h; Autoclave; optical yield given as %ee; enantioselective reaction; |
97 % ee | With hydrogen In methanol at 20℃; for 0.5h; | 11 [Example 11] Asymmetric hydrogenation reaction: The organic inorganic composite material 2-13 (50 mg) and 2 mg (4.9 mmol) of bis(cyclooctadiene)rhodium (I) tetrafluoroborate were stirred in 3 ml of methanol at room temperature for 30 minutes in a hydrogen atmosphere of 1 atm. 105 mg (0.51 mmol) of α-(acetoamido)cinnamic acid was added to the resulting mixture, and reaction was conducted at room temperature for 30 minutes. Thus, N-acetyl-phenylalanine was obtained. An enantiomer excess of D-form determined by HPLC analysis (Chirace AD-H, manufactured by Daicel) was 97% e.e. |
With (R,R)-1,2-bis(tert-butylmethylphosphino)benzene(1,5-cyclooctadiene)-rhodium(I) hexafluoroantiomonate; hydrogen In methanol at 20℃; for 0.5h; optical yield given as %ee; enantioselective reaction; | ||
With BF4(1-)*C49H54O4P2Rh(1+); hydrogen In dichloromethane at 20℃; for 18h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | ||
With (R)-2-(tert-butylmethylphosphino)-3-(di-tertbutylphosphino)quinoxaline(1,5-cyclooctadiene)rhodium(I) hexafluoroantimonate; hydrogen In methanol at 20℃; for 18h; enantioselective reaction; | ||
97 % ee | With bis(norbornadiene)rhodium(l)tetrafluoroborate; (RC,SFc,SP)-1-[2-(1-N,N-dimethylaminoethyl)ferrocen-1-yl]phenylphosphino-1'-di-iso-propylphosphinoferrocene; hydrogen In tetrahydrofuran at 25℃; for 2h; enantioselective reaction; | |
With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; C56H38O4P2; hydrogen In dichloromethane at 20℃; for 20h; Schlenk technique; Autoclave; Inert atmosphere; enantioselective reaction; | ||
99 % ee | With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; 1-(3-(phenyl(o-tolyl)phosphanyl)phenyl)urea; hydrogen In methanol; ethanol at 0℃; for 5h; Inert atmosphere; Autoclave; | |
95 % ee | With di[(η-1,2,5,6)-1,5-cyclooctadiene] rhodium hexafluoroantimonate; hydrogen In tetrahydrofuran at 25℃; for 16h; Inert atmosphere; Autoclave; enantioselective reaction; | |
With C34H37Au2Cl2NO2P2; hydrogen In methanol at 80℃; for 24h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With TEA; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole, Et3N / CHCl3 2: 0.6N aq. HCl / dioxane / Ambient temperature 3: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole / CHCl3 4: 0.6N aq. HCl / dioxane / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole / CH2Cl2 / Ambient temperature 2: aq. HCl / dioxane / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 46 percent / TsOH*H2O, N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole / dimethylformamide / Ambient temperature 2: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole / CH2Cl2 / Ambient temperature 3: aq. HCl / dioxane / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole, Et3N / CHCl3 2: H2, HOAc / 10percent Pd/C / H2O / 760 Torr / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole, Et3N / Ambient temperature 2: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole 3: H2, HOAc / 10percent Pd/C / H2O / 760 Torr / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole, Et3N / CHCl3 2: H2, HOAc / 10percent Pd/C / H2O / 760 Torr / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole, Et3N / CHCl3 2: H2, HOAc / 10percent Pd/C / H2O / 760 Torr / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole, Et3N / CHCl3 2: 0.6N aq. HCl / dioxane / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 46 percent / TsOH*H2O, N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole / dimethylformamide / Ambient temperature 2: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole / CH2Cl2 / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole, Et3N / Ambient temperature 2: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole, Et3N / CHCl3 2: 0.6N aq. HCl / dioxane / Ambient temperature 3: N,N'-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole / CHCl3 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: N-methylmorpholine (NMM) / tetrahydrofuran / 0.03 h / -15 °C 2: N-methylmorpholine (NMM) / tetrahydrofuran / 1.) -15 deg C, 2.) from -15 deg C to RT, 2 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 70 percent / DCC, HOBt / CH2Cl2 / 18 h / Ambient temperature 2: H2 / 10percent Pd/C / methanol / 6 h / 760 Torr / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 70 percent / DCC, HOBt / CH2Cl2 / 18 h / Ambient temperature 2: H2 / 10percent Pd/C / methanol / 6 h / 760 Torr / Ambient temperature 3: 43 percent / DCC, HOBt / acetonitrile / 18 h / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | In methanol at 20℃; for 4h; Heating / reflux; | 4b; 5.5.2 2 L 3-necked round bottom flask equipped with a mechanical stirrer, thermometer, and condenser was charged with S-enriched methyl 3-AMINO-3- (3, 4- dimethoxyphenyl) -propionate (70.9 g, 0.296 mol), N-acetyl-D-phenylalanine (47.9, 0.231 mol), and methanol (1,060 mL). The stirred slurry was heated to reflux and held at reflux for 1 hour. The stirred mixture was allowed to cool to ambient temperature and stirring was continued for another 3 hours at ambient temperature. The slurry was filtered and the filter cake was rinsed with methanol (290 mL). The solid was air-dried and then dried in vacuo at 55°C to a constant weight, affording 85.0 g (82% yield) of (S)-methyl 3-AMINO-3- (3, 4- DIMETHOXYPHENYL)-PROPIONATE N-acetyl-D-phenylalanine salt (90.7% EE). Chiral HPLC (10/90 MeOH/aq HC104 &COMMAT;PH 1.0, Daicel Crownpak CR (+) column, 4 x 150 mm, 5µm, 0.7 mL/min. , 240 nm) : 22.5 min. (R-isomer, 4.5% by area), 27.15 min. (S-isomer, 92.7% by AREA). 1H NMR (DMSO-D6) 8 : 7.88 (d, 1H), 7.14-7. 27 (m, 5H), 7.07 (s, 1H), 6.89 (s, 2H), 4.25-4. 33 (m, 2H), 3.74 (s, 3H), 3.72 (s, 3H), 3.56 (s, 3H), 3.01-3. 09 (dd, 1H), 2.66-2. 86 (m, 3H), 1.76 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.2% | 10 Asymmetric hydrogenation of (Z)-2-acetamidocinnamic acid catalyzed by [Rh(COD)(R-1a)]Cl complex EXAMPLE 10 Asymmetric hydrogenation of (Z)-2-acetamidocinnamic acid catalyzed by [Rh(COD)(R-1a)]Cl complex The hydrogenation proceeded through the same procedure as example 9 using Rh(COD)(R-1a)Cl (prepared in example 6) instead of Rh(COD)(S-1a)Cl (prepared in example 5) to give the product (R)-2-acetamido-3-phenylpropanoic acid in 96.2% yield and 81.6% e.e. (The enantiomeric excess was determined by the same method as in Example 9.) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; acetic anhydride In water | 1 N-Acetyl-D-phenylalanine EXAMPLE 1 N-Acetyl-D-phenylalanine To a stirred solution of 20.0 parts of D-phenylalanine in 121 parts of water, cooled to about 1°-2°, is added, portionwise, an aqueous 50% sodium hydroxide solution until pH 12 is reached. Then 37 parts of acetic anhydride is added, while continuously adding aqueous 50% sodium hydroxide to keep the pH at about 12 and cooling the solution to keep the temperature at between about 10° to 30°. After about 20 minutes the mixture is acidified to pH 1 with concentrated hydrochloric acid and filtered. The recovered solid is recrystallized from water to afford N-acetyl-D-phenylalanine, melting at about 170°-172°. | |
With sodium hydroxide; acetic anhydride In water | 1 N-Acetyl-D-phenylalanine EXAMPLE 1 N-Acetyl-D-phenylalanine To a stirred solution of 20.0 parts of D-phenylalanine in 121 parts of water, cooled to about 1° -2°, is added, portionwise, an aqueous 50% sodium hydroxide solution until pH 12 is reached. Then 37 parts of acetic anhydride is added, while continuously adding aqueous 50% sodium hydroxide to keep the pH at about 12 and cooling the solution to keep the temperature at between about 10° to 30°. After about 20 minutes the mixture is acidified to pH 1 with concentrated hydrochloric acid and filtered. The recovered solid is recrystallized from water to afford N-acetyl-D-phenylalanine, melting at about 170°-172°. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.79 g (100%) | 108.a 108a. 108a. 1-(2-(R)-Acetylamino-3-phenyl-propionyl)-pyrrolidin-2-(S)-carboxylic acid benzyl ester Reaction of 0.42 g of (D)-N-acetyl-phenylalanine and of 0.49 g (L)-proline benzyl ester hydrochloride according to the procedure described for example 91b afforded 0.79 g (100%) of the title compound as a yellow oil. (+)-APCI-MS: 395 (MH+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; hexane; dichloromethane; | The resulting (R)-N-acetylphenylalanine in an amount of 2 mg was dissolved in 0.5 mL of methanol and 0.5 mL of dichloromethane, and the solution was added with a 10% solution of trimethylsilyldiazomethane in n-hexane until the solution colored in yellow to obtain the methyl ester compound. Examples 24 to 28Preparation of Optically Active N-Acetylphenylalanine Using Rhodium Metal Complex CatalystThe target compounds were synthesized in the same manner as that of Example 23 except for the metal complex catalyst. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | In chloroform Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With sodium hydroxide; water at 0℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 62% 2: 35% | In isopropyl alcohol at 40 - 50℃; for 5h; | 2 In a 250 ml three-necked flask equipped with a mechanical stirrer, a condenser and a thermometer, 6 g (30.8 mmol, 1 mol. eq.) of racemic 1-benzyl-2,2-dimethoxyethylamine and 3.18 g (15.4 mmol, 0.5 mol. eq.) of N-acetyl-(D)-phenylalanine (Sigma Aldrich) are introduced into 94 g of isopropanol (solution at 6%). The medium is stirred and heated at 500C for 3 h, and then a temperature hold is performed at 400C for 2 h. At the end of this hold, the temperature is allowed to return to ambient temperature slowly and stirring is continued overnight at this temperature.The precipitate is filtered off under vacuum and the solid is washed with 100 ml of cyclohexane (filtrate 1 ), and then oven-dried at 40°C under vacuum. A mass of 3.85 g of (S)-1-benzyl-2,2-dimethoxyethylammonium N-acetyl-(D)-phenylalaninate is obtained, 2008 FR403 (WA) 19i.e. a yield of 62% relative to the N-acetyl-(D)-phenylalanine.The solid is taken up in 66 g of isoopropanol (solution at 5.5%) and the medium is heated at 500C for approximately 1 h 30. The temperature is allowed to return to ambient temperature slowly and the medium is maintained at this temperature overnight with stirring. After filtration, the solid is washed with 50 ml of cyclohexane and oven-dried at 400C.The solid is treated with an aqueous solution of sodium hydroxide and the aqueous phase is extracted with CH2CI2. After concentration of the solvent, 1.32 g of (S)-1- benzyl-2,2-dimethoxyethylamine are obtained, i.e. a yield of 44% relative to the N- acetyl-(D)-phenylalanine, with an optical purity equal to: ee(S) ≥99% (determined by chiral HPLC).The filtrate 1 is concentrated and the solid residue is stirred in approximately 100 ml of cyclohexane, filtered under vacuum and washed with 60 ml of cyclohexane. After drying, the precipitate (1 g, i.e. a yield of 35% relative to the N-acetyl-(D)- phenylalanine) is taken up in 37 g of isoPrOH (5.5% dilution) and the medium is kept stirring for 1 h 30. After filtration, drying of the solid and basic treatment, 0.66 g of optically active (R)-1-benzyl-2,2-dimethoxyethylamine is obtained with an optical purity equal to: ee(R)=91 % (determined by chiral HPLC), i.e. a yield of 22% relative to the N- acetyl-(D)-phenylalanine.(S)-1-benzyl-2,2-dimethoxyethylammonium N-acetyl-(D)-phenylalaninate (white solid)(compound of formula (VII) - R1 = R2= methyl, R3 = R7 = benzyl, P = acetyl)Molecular formula: C22H30N2Os Molar mass: 402.49 g.mol'1- NMR (200MHz/DMSO-d6):1H NMR: δ 1.78 (s, 3H, CH3); 2.63-2.74 and 3.05-3.14 (syst. AB, 2H, CH2); 2.79-2.92 (m, 2H, CH2); 3.2-3.4 (m, 1 H, CH); 3.33 (s, 3H, CH3), 3.38 (s, 3H, CH3), 4.2 (d, J=4.8Hz, 1 H, CH), 4.32 (m, 1 H, CH); 5.1 1 (broad s, NH3+); 7.1-7.4 (m, 10H, Haromatιc) and 7.86 (d, 1 H, NH) ppm. 2008FR403 (WA) 2013C NMR: δ 22.56 (CH3); 36.06 (CH2); 37.31 (CH2); 53.36 (CH); 54.51 (CH); 54.85 (CH3); 55.12 (CH3); 105.25 (CH), 125.95-126.23-127.88-128.27- 129.16-129.29 (CHaromatlc); 137.96-138.59 (CarOmat,c), 168.66 (C=O) and 173.71 (C=O) ppm.- Melting point: Mp=159°C- Optical rotation: α25D= -39.6° (MeOH, c=1 ) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; triethylamine In dichloromethane at 20℃; for 18h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; triethylamine In dichloromethane at 20℃; for 18h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; triethylamine / dichloromethane / 18 h / 20 °C / Inert atmosphere 2: methanol; sodium methylate / 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With benzotriazol-1-ol; dicyclohexyl-carbodiimide In 1,4-dioxane; ethyl acetate at 0 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dicyclohexyl-carbodiimide In dichloromethane at 0℃; for 3.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: dicyclohexyl-carbodiimide / dichloromethane / 3.5 h / 0 °C 2: sodium hydrogen sulfide monohydrate / methanol / 2.58 h / 20 °C 3: copper(II) acetate monohydrate; benzotriazol-1-ol / N,N-dimethyl-formamide / 0.58 h / 20 °C 4: water; trifluoroacetic acid / 1.5 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: dicyclohexyl-carbodiimide / dichloromethane / 3.5 h / 0 °C 2: sodium hydrogen sulfide monohydrate / methanol / 2.58 h / 20 °C 3: copper(II) acetate monohydrate; benzotriazol-1-ol / N,N-dimethyl-formamide / 0.58 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | In methanol; water; at 50℃; | Into a 250 mL round-bottomed flask equipped with a stirrer, reflux condenser and thermometer was added O-methyl-D,L-serine (5 g) in 90:10 methanol/water (25 mL). N-Acetyl-D-phenylalanine (8.70 g) was added in one portion and the mixture heated to 50C overnight. The suspension was cooled to room temperature and filtered, and the solid was rinsed with 90:10 methanol/water (5 mL) and dried at 40C under vacuum for 3 h. The N-acetyl-D-phenylalanine salt of O-methyl-D-serine (3.4 g, 25%) was obtained as a white solid with a chiral purity >90%. Regeneration of the title compound could be effected by adjustment of the pH to 1-2 by treatment with HCl, followed by extraction into an organic solvent and subsequent adjustment of the pH to ?7 with NaOH. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With benzotriazol-1-ol; O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 23℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | In ethanol Reflux; | P1 (3R, 4S)-4-Aminotetrahydro-2H -pyran-3-ol, N -acetyl-D-phenylalanine salt (P1) trans-4-Aminotetrahydro-2H-pyran-3-ol (30.0 g, 256 mmol) and N-acetyl-Dphenylalanine (99%, 53.6 g, 256 mmol) were suspended in ethanol (3 L), equallydivided between two flasks. The mixtures were heated at reflux until they became homogeneous; at this point the volume in each flask had been reduced to approximately 1.3 L. After the solutions had cooled to room temperature, the precipitates were isolated via filtration and washed with ethanol to provide a white solid (38 g). This material was suspended in ethanol (900 mL) and heated at reflux for 30minutes, during which time the volume was reduced to approximately 800 mL. The mixture was cooled first to room temperature, and then in an ice bath for 30 minutes, whereupon the solid was collected via filtration to provide the product as a white solid. Yield: 36.0 g, 111 mmol, 43%. H NMR (400 MHz, DMSO-d6) ö 7.62 (d, J=7.8 Hz, 1H), 7.11-7.26 (m, 5H), 4.15-4.24 (m, 1H), 3.71-3.82 (m, 2H), 3.20-3.35 (m, 2H), 3.04 (dd,J=13.6, 4.8 Hz, 1H), 2.93 (dd, J=10.5, 10.3 Hz, 1H), 2.71-2.86 (m, 2H), 1.79-1.87 (m,1H), 1.75 (5, 3H), 1.39-1.52 (5, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With N,N'-diethylurea; copper(II) bis(trifluoromethanesulfonate); triethylamine In tetrahydrofuran at 50℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol | 4.3. Titration Experiments General procedure: Tetrabutylammonium (TBA) salts of examinate anions were prepared before every titration experiments, namelycommercially available carboxylic acids was dissolved in 0.5 mL of dry methanol and 1 equivalent of TBAOH(solution in methanol, c=1.21 M) was added. Prior to the experiment, the salts were pre-dried overnight underhigh vacuum at 60°C. To obtain the appropriate water concentration distilled water was added to thecommercially available DMSO-d6 or acetone-d6 of 99.9% isotopic purity (purchased from ARMAR AG), andanalyzed using Karl Fisher water titration. All titration experiments was performed on Bruker (400 MHz) at 298K. | |
In methanol for 0.166667h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | Stage #1: (R)-N-acetylphenylalanin With N-ethyl-N,N-diisopropylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In dichloromethane at 20℃; for 0.5h; Inert atmosphere; Stage #2: C33H29N5O5S*C2HF3O2 In dichloromethane at 20℃; for 5h; Inert atmosphere; | Typical procedure C for amide coupling: General procedure: To a CH2Cl2 solution ofappropriate N-acetylated amino acid (2.0 eq) and HATU (3.0 eq) wasadded DIPEA (4.5 eq) under argon atmosphere. The reaction mixturewas stirred at room temperature for 30 min, then was added CH2Cl2suspension of Boc-deprotected Arg analog TFA salt (1.0 eq) with DIPEA (1.5 eq). The reaction mixture was stirred at room temperature for 5 h. Asaturated aqueous sodium bicarbonate solution was added to themixture to quench the reaction. The organic layer was diluted by EtOAcand extracted by water and brine, then combined organic layer wasdried over MgSO4, filtered, and concentrated under reduced pressure.The residue was purified by flash column chromatography (eluting withhexane/EtOAc) on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tetrahydroxydiboron; [Rh(OH)(cod)]2 In ethanol at 50℃; for 18h; Schlenk technique; Inert atmosphere; |
[ 2752-35-4 ]
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Code | Phrase |
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Code | Phrase |
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P322 | |
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P378 | |
P380 | Evacuate area. |
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P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
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P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
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P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
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P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
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Disposal | |
Code | Phrase |
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Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
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H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
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H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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