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Example 59; Asymmetric hydrogenation of itaconic acid [Show Image] Under an argon atmosphere, to bis(eta2,eta2-1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate (1.0 mg, 0.0021 mmol) and (S)-2,2'-bis[bis(4-dimethylaminophenyl)phosphino]-1,1'-binaphthyl (4.6 mg, 0.0058 mmol) synthesized in Reference Example 8 was added methanol (4 mL), and the mixture was stirred for 30 min. The reaction mixture was added to a solution of itaconic acid (21.8 mg, 0.168 mmol) in methanol (1 mL), and the mixture was subjected to hydrogenation under a 1 MPa hydrogen pressure at 25C for 15 hr. 2 mL of the reaction mixture was taken, sulfuric acid was added and the mixture was refluxed at 85C for 1 hr. The methylated solution was analyzed by gas chromatography (column: betaDEX-225 (0.25 mm i.d. × 30 m, 0.25 mum)) to find a conversion ratio of 100%, and an optical purity of 56.2%ee. Examples 60-63 According to the method of Example 59, the reaction was carried out using the optically active ligands of Examples 3, 6, 12 and 15. The results are shown in Table 2. |
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Example 59; Asymmetric hydrogenation of itaconic acid [Show Image] Under an argon atmosphere, to bis(eta2,eta2-1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate (1.0 mg, 0.0021 mmol) and (S)-2,2'-bis[bis(4-dimethylaminophenyl)phosphino]-1,1'-binaphthyl (4.6 mg, 0.0058 mmol) synthesized in Reference Example 8 was added methanol (4 mL), and the mixture was stirred for 30 min. The reaction mixture was added to a solution of itaconic acid (21.8 mg, 0.168 mmol) in methanol (1 mL), and the mixture was subjected to hydrogenation under a 1 MPa hydrogen pressure at 25C for 15 hr. 2 mL of the reaction mixture was taken, sulfuric acid was added and the mixture was refluxed at 85C for 1 hr. The methylated solution was analyzed by gas chromatography (column: betaDEX-225 (0.25 mm i.d. × 30 m, 0.25 mum)) to find a conversion ratio of 100%, and an optical purity of 56.2%ee. Examples 60-63 According to the method of Example 59, the reaction was carried out using the optically active ligands of Examples 3, 6, 12 and 15. The results are shown in Table 2. |
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Example 59; Asymmetric hydrogenation of itaconic acid [Show Image] Under an argon atmosphere, to bis(eta2,eta2-1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate (1.0 mg, 0.0021 mmol) and (S)-2,2'-bis[bis(4-dimethylaminophenyl)phosphino]-1,1'-binaphthyl (4.6 mg, 0.0058 mmol) synthesized in Reference Example 8 was added methanol (4 mL), and the mixture was stirred for 30 min. The reaction mixture was added to a solution of itaconic acid (21.8 mg, 0.168 mmol) in methanol (1 mL), and the mixture was subjected to hydrogenation under a 1 MPa hydrogen pressure at 25C for 15 hr. 2 mL of the reaction mixture was taken, sulfuric acid was added and the mixture was refluxed at 85C for 1 hr. The methylated solution was analyzed by gas chromatography (column: betaDEX-225 (0.25 mm i.d. × 30 m, 0.25 mum)) to find a conversion ratio of 100%, and an optical purity of 56.2%ee. Examples 60-63 According to the method of Example 59, the reaction was carried out using the optically active ligands of Examples 3, 6, 12 and 15. The results are shown in Table 2. |
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Beispiel 6 : Herstellung der Rh-Komplexes Zu einer Loesung von 1 mmol des Diphosphines (Beispiel 5) in 2 [ML] THF werden 1 mmol [Rh (COD) acac] gegeben und die Loesung 15 min geruehrt. Im Anschluss wird eine aequimolare Menge 40% ige [TETRAFLUORBORONSaeURE] zugegeben und weitere 15 min geruehrt. Der Metallkomplex wird durch Zugabe von 20 ml Ether ausgefaellt, durch Zugabe von 0.5 [ML DICHLORMETHAN] wieder geloest und durch Zugabe von Ether erneut ausgefaellt. Der Metallkomplex wird abfiltriert und im Vakuum getrocknet. [P-NMR (CDC13)] : [8 = 22.] 3 (dd), 16.7 (dd) ppm. Beispiel 7 : Hydrierungen Alle Hydrierungen wurden bei [25C] unter einem Wasserstoffdruck von 1 bar in 15 ml Loesungsmittel durchgefuehrt. Substrat und Katalysator (Beispiel 6) wurden im Verhaeltnis 100 : 1 eingesetzt. |
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Beispiel 6 : Herstellung der Rh-Komplexes Zu einer Loesung von 1 mmol des Diphosphines (Beispiel 5) in 2 [ML] THF werden 1 mmol [Rh (COD) acac] gegeben und die Loesung 15 min geruehrt. Im Anschluss wird eine aequimolare Menge 40% ige [TETRAFLUORBORONSaeURE] zugegeben und weitere 15 min geruehrt. Der Metallkomplex wird durch Zugabe von 20 ml Ether ausgefaellt, durch Zugabe von 0.5 [ML DICHLORMETHAN] wieder geloest und durch Zugabe von Ether erneut ausgefaellt. Der Metallkomplex wird abfiltriert und im Vakuum getrocknet. [P-NMR (CDC13)] : [8 = 22.] 3 (dd), 16.7 (dd) ppm. Beispiel 7 : Hydrierungen Alle Hydrierungen wurden bei [25C] unter einem Wasserstoffdruck von 1 bar in 15 ml Loesungsmittel durchgefuehrt. Substrat und Katalysator (Beispiel 6) wurden im Verhaeltnis 100 : 1 eingesetzt. |
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With hydrogen;Rh-complex of (R,R)-DiPAMP; In methanol; at 20℃; under 760.051 Torr; for 0.666667h;Product distribution / selectivity; |
To a solution of the substrate (0.5 mmol) in MeOH (7 ml), a solution of the Rh-L* catalyst in MeOH (prepared as above) is added under Ar, then a vacuum/H2 cycle is applied. The mixture is stirred at room temperature under 1 atm of H2 (10 bars for atropic acid) until uptake H2 ceased. The solution is analyzed by GC on Lipodex E, Chiralsil-L-Val, CP-Chiralsil DEX CB columns. The acids were esterified in CH2Cl2 using TMSCH2N2 (hexanes) prior to analysis 25 (Tables 4, 5 and 6). The results show that using the ligands of the present invention, it is possible to significantly increase the reaction rate and the ee of the product. |
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With hydrogen;[(eta2-1,2,5,6)-1,5-cyclooctadiene][(Sp,S)-cis-2-(2-diphenylphosphinoethyl-kappaP)-(1-phenylphospholane-kappaP)]rhodium(I)hexafluoroantimonate; In methanol; at 20℃; for 3h;Product distribution / selectivity; |
In a glove box, an autoclave with a 20 mL glass tube insert equipped with a magnetic stirring bar was charged with the hydrogenation substrate (1 mmol), anhydrous degassed solvent (7 mL) and the metal complex pre-catalyst (0.01 mmol). After 10 cycles of evacuation and filling with hydrogen, the autoclave was pressurised to an appropriate initial pressure of hydrogen. The reaction mixture was stirred at room temperature and after the appropriate time the autoclave was opened, the reaction mixture was filtered through silica gel, concentrated and the residue was analysed by enantioselective GC. |
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With hydrogen;[(eta2-1,2,5,6)-1,5-cyclooctadiene][(Sp,R)-trans-2-(2-diphenylphosphinoethyl-kappaP)-(1-phenylphospholane-kappaP)]rhodium(I)hexafluoroantimonate; In methanol; at 20℃; for 3h;Product distribution / selectivity; |
In a glove box, an autoclave with a 20 mL glass tube insert equipped with a magnetic stirring bar was charged with the hydrogenation substrate (1 mmol), anhydrous degassed solvent (7 mL) and the metal complex pre-catalyst (0.01 mmol). After 10 cycles of evacuation and filling with hydrogen, the autoclave was pressurised to an appropriate initial pressure of hydrogen. The reaction mixture was stirred at room temperature and after the appropriate time the autoclave was opened, the reaction mixture was filtered through silica gel, concentrated and the residue was analysed by enantioselective GC. |
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With hydrogen;[(eta2-1,2,5,6)-1,5-cyclooctadiene][(Sp,R,R)-trans-2-(2-diphenylphosphino-2-methylethyl-kappaP)-(1-phenylphospholane-kappaP)]rhodium(I)hexafluoroantimonate; In methanol; at 20℃; for 3h;Product distribution / selectivity; |
In a glove box, an autoclave with a 20 mL glass tube insert equipped with a magnetic stirring bar was charged with the hydrogenation substrate (1 mmol), anhydrous degassed solvent (7 mL) and the metal complex pre-catalyst (0.01 mmol). After 10 cycles of evacuation and filling with hydrogen, the autoclave was pressurised to an appropriate initial pressure of hydrogen. The reaction mixture was stirred at room temperature and after the appropriate time the autoclave was opened, the reaction mixture was filtered through silica gel, concentrated and the residue was analysed by enantioselective GC. |
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With hydrogen;[(eta2-1,2,5,6)-1,5-cyclooctadiene][(Sp,R,S)-trans-2-(2-diphenylphosphino-2-methylethyl-kappaP)-(1-phenylphospholane-kappaP)]rhodium(I)hexafluoroantimonate; In tetrahydrofuran; at 20℃; for 3h;Product distribution / selectivity; |
In a glove box, an autoclave with a 20 mL glass tube insert equipped with a magnetic stirring bar was charged with the hydrogenation substrate (1 mmol), anhydrous degassed solvent (7 mL) and the metal complex pre-catalyst (0.01 mmol). After 10 cycles of evacuation and filling with hydrogen, the autoclave was pressurised to an appropriate initial pressure of hydrogen. The reaction mixture was stirred at room temperature and after the appropriate time the autoclave was opened, the reaction mixture was filtered through silica gel, concentrated and the residue was analysed by enantioselective GC. |
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With hydrogen;[(eta2-1,2,5,6)-1,5-cyclooctadiene][(Sp,R)-trans-2-(2-diphenylphosphinoethyl-kappaP)-(1-phenylphospholane-kappaP)]rhodium(I)tetrafluoroborate; at 20℃; for 3h;Product distribution / selectivity; |
In a glove box, an autoclave with a 20 mL glass tube insert equipped with a magnetic stirring bar was charged with the hydrogenation substrate (1 mmol), anhydrous degassed solvent (7 mL) and the metal complex pre-catalyst (0.01 mmol). After 10 cycles of evacuation and filling with hydrogen, the autoclave was pressurised to an appropriate initial pressure of hydrogen. The reaction mixture was stirred at room temperature and after the appropriate time the autoclave was opened, the reaction mixture was filtered through silica gel, concentrated and the residue was analysed by enantioselective GC. |
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With hydrogen;[(eta2-1,2,5,6)-1,5-cyclooctadiene][(Sp,S)-cis-2-(2-diphenylphosphinoethyl-kappaP)-(1-phenylphospholane-kappaP)]rhodium(I)tetrafluoroborate; at 20℃; for 3h;Product distribution / selectivity; |
In a glove box, an autoclave with a 20 mL glass tube insert equipped with a magnetic stirring bar was charged with the hydrogenation substrate (1 mmol), anhydrous degassed solvent (7 mL) and the metal complex pre-catalyst (0.01 mmol). After 10 cycles of evacuation and filling with hydrogen, the autoclave was pressurised to an appropriate initial pressure of hydrogen. The reaction mixture was stirred at room temperature and after the appropriate time the autoclave was opened, the reaction mixture was filtered through silica gel, concentrated and the residue was analysed by enantioselective GC. |
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With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (2S,4S)-N-butoxycarbonyl-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine; In water; at 30℃; under 825.083 Torr;Catalytic behavior; |
General procedure: The set up of the hydrogenation apparatus [22,23] is shown in Scheme 4. About 1.0-1.4 g of the yellow-orange sol gel immobilized catalyst, a desired amount of substrate and 95 mL of solvent (methanol, water or aqueous-micellar solution) were added to a stirred tank reactor and stirred at 400 rpm under N2-atmosphere at the desired reaction temperature. The N2 was replaced by H2 (p = 1.1 × 105 Pa) without stirring and the reaction was started by turning the stirrer on 800 rpm again. The reactions were performed in semi-batch mode with hydrogen being permanently added to the stirred tank reactor to achieve a constant total pressure of 1.1 × 105 Pa in reactor. The cumulative hydrogen consumption and the pressure during the reaction were recorded using a Bronkhorst flow meter and pressure controller (Bronkhorst Maettig GmbH, Kamen, Germany), respectively (see Scheme 4). The sensitivity of measured hydrogen consumption was ±0.4 mL. The pressure and the hydrogen flow during the reaction were registered and analyzed on a PC, from these results the substrate concentration csubstrate and the conversion X were calculated. |
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With C18H16F6N2O4Pd; hydrogen; benzylamine; In 2,2,2-trifluoroethanol; at 20℃; under 5171.62 Torr; |
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. |
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