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Chiral organic, inorganic polymer assembled catalyst, synthesis method and use

A technology of catalysts and compounds, which is applied in a class of chiral organic-inorganic polymer assembly catalysts, synthesis and applications, and can solve the problems of complex synthesis of polymer ligands and low loading of catalytically active species

Inactive Publication Date: 2007-04-11
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0013] In the first loading mode, the ligands or active units are randomly loaded on the disordered polymer support, resulting in a lower loading of catalytically active species, while the stereoselectivity and catalytic efficiency of the catalyst are comparable to those of unsupported The corresponding homogeneous systems will be reduced to varying degrees; [[de Vos, D.E.; Vankelecom, I.F.J.; Jacobs, P.A., Eds.In Chiral Catalyst Immobilization and Recycling; Wiley-VCH: Weinheim, 2000.] The second mode It makes up for the shortcomings of the first mode and improves the loading capacity, catalytic activity and selectivity of the catalyst. There have been some successful reports in recent years, but relatively speaking, the synthesis of polymer ligands in this mode is cumbersome.

Method used

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  • Chiral organic, inorganic polymer assembled catalyst, synthesis method and use
  • Chiral organic, inorganic polymer assembled catalyst, synthesis method and use
  • Chiral organic, inorganic polymer assembled catalyst, synthesis method and use

Examples

Experimental program
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Embodiment 1

[0073] Example 1: In a dry 25mL standard Schlenk bottle, under argon protection, compound 7a (0.57g), hexamethylphosphinetriamine (0.46mL), and anhydrous toluene (5mL) were added, stirred and heated to reflux for 9h, Heating was stopped and cooled to room temperature, the solvent was evaporated under reduced pressure, and column chromatography (n-hexane:ethyl acetate=10:1) gave a white foamy solid, which was recrystallized from ether to give compound 8a (0.6g). 83.5% yield.[α] D 20=650.1°(c 1.0, CHCl3).IR(KBr): 3055, 2800, 1621, 1588, 1504, 1462, 1330, 1293, 1232, 1207, 1189, 1076, 983, 944, 821, 780, 749, 692 , 678 cm-1.1H NMR (300MHz, CDCl3): δ8.24-8.26 (m, 2H), 7.94-8.08 (m, 6H), 7.64-7.71 (m, 2H), 7.39-7.58 (m, 10H) , 7.29-7.37 (m, 2H), 2.58-2.62 (m, 12H).31P NMR (121MHz, CDCl3) δ149.87 ppm. MS (ESI): (M+H), 717.35; HRMS (MALDI): calcd .forC44H35N2O4P2: 717.2072; Found: 717.2053.

Embodiment 2

[0074] Example 2: In a dry 25mL standard Schlenk bottle, under argon protection, compound 7b (0.65g), hexamethylphosphinetriamine (0.46mL) and anhydrous toluene (5mL) were added, stirred and heated to reflux for 12h, Heating was stopped and cooled to room temperature, the solvent was evaporated under reduced pressure, and column chromatography (n-hexane: ethyl acetate = 10:1) gave a white foamy solid, which was recrystallized from ether to give compound 8b (0.62 g). 78.5% yield.[α] D 20 =500.6° (c 1.0, CHCl 3 ).IR(KBr): 3054, 2799, 1590, 1494, 1464, 1333, 1292, 1232, 1208, 1047, 984, 945, 819, 790, 749, 693cm -1.1 H NMR (300MHz, CDCl 3 ): δ8.18(s, 2H), 7.91-8.06(m, 6H), 7.82(s, 4H), 7.26-7.62(m, 14H), 2.55-2.59(m, 12H). 31 P NMR (121MHz, CDCl 3 )δ149.87ppm. MS (ESI): (M+H), 793.55; HRMS (MALDI): calcd.for C 50 h 39 N 2 o 4 P 2 : 793.2385; Found: 793.2379.

Embodiment 3

[0075] Example 3: In a dry 25mL standard Schlenk bottle, under argon protection, compound 7c (0.65g), hexamethylphosphinetriamine (0.46mL), anhydrous toluene (5mL) were added, stirred and heated to reflux for 12h, Heating was stopped and cooled to room temperature, the solvent was evaporated under reduced pressure, and column chromatography (n-hexane:ethyl acetate=10:1) gave a white foamy solid, which was recrystallized from ether to give compound 8c (0.67g). 85.0% yield.[α] D 20 =485.0°(c 1.0, CHCl 3 ).IR (KBr): 3054, 2799, 1621, 1588, 1505, 1463, 1332, 1292, 1232, 1207, 1188, 1155, 1075, 984, 945, 884, 820, 796, 749, 693cm -1.1 HNMR (300MHz, CDCl 3 ): 8.18-8.19(m, 2H), 7.91-8.05(m, 7H), 7.69-7.71(m, 2H), 7.41-7.65(m, 13H), 7.29-7.34(m, 2H), 2.55-2.59 (m, 12H). 31 P NMR (121MHz, CDCl 3 )δ149.48 ppm. MS (ESI): (M+H), 793.35; HRMS (MALDI): calcd.forC 50 h 39 N 2 o 4 P 2 : 793.2385; Found: 793.2379.

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Abstract

A chiral organic-inorganic high-molecular assembly used as catalyst for preparing alpha-amino acid and its derivative, chiral amine and its derivative and 2-alkyl-1,4-butanedioic acid and its derivative from alpha-dehydroamino acid and its derivative, enamine and itaconic acid and their derivatives through asymmetric catalytic hydrogenation is prepared from P-contained chiral ligand and transition metal's ions through coordination.

Description

technical field [0001] The invention relates to a novel ligand, a chiral catalyst and a loading method and application of the chiral catalyst. Using phosphorus-containing chiral ligands and transition metal ions to form organic-inorganic polymer assemblies through coordination, the metal ions in the assemblies provide catalytic centers, and the ligands provide chiral environments. The advantage is that these assemblies are insoluble in common Organic solvents, thus providing a new way for heterogeneous asymmetric catalysis, because this type of heterogeneous chiral catalyst does not use any other organic or inorganic support, so it is called self-supporting chiral catalyst. The catalyst can be used for asymmetric catalytic hydrogenation of α-dehydroamino acid and its derivatives, various enamines, itaconic acid and its derivatives and other compounds. The asymmetric catalytic hydrogenation of the above compounds can be used in the synthesis of compounds such as α-amino acids ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/6571B01J31/18C07B35/02B01J31/02
CPCY02P20/50
Inventor 丁奎岭王兴旺
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI