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Planar chiral double-reactive center ruthenium catalyst and synthesis and application thereof

A ruthenium catalyst and dual-reaction technology, which are applied to the ruthenium catalyst and its synthesis and application, the chiral double-reaction center ruthenium catalyst and its synthesis, and the application fields of asymmetric hydrogenation of β-aminoketone compounds, which can solve the problem of catalysts. Ligand synthesis is complex, it cannot be stably stored, and the cost of metal rhodium is high. It achieves good industrial application prospects, convenient storage and use, and good catalytic effect.

Active Publication Date: 2014-09-24
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the synthesis of the catalyst ligand is relatively complicated, the cost is high, and it cannot be stored stably.
In addition, many chiral catalysts have been developed for the asymmetric hydrogenation of ketones, such as Zhang Xumu and others published in "Angew. In the Practical Synthesis of Enantiopureγ-Amino Alcohols by Rhodium-Catalyzed Asymmetric Hydrogenation ofβ-Secondary-Amino Ketones article on the page, it is mentioned that the asymmetric hydrogenation of ketones can be achieved using the chiral ligand Rh-DuanPhos catalyst; but this type of system does not Excellent selectivity, and the cost of metal rhodium is relatively high, so it is difficult to apply to industrial production

Method used

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  • Planar chiral double-reactive center ruthenium catalyst and synthesis and application thereof
  • Planar chiral double-reactive center ruthenium catalyst and synthesis and application thereof
  • Planar chiral double-reactive center ruthenium catalyst and synthesis and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0059] Synthesis of Hilarochiral Double Reaction Center Ruthenium Catalysts

[0060] Tris(triphenylphosphine)ruthenium dichloride (3.8 mg, 4 μmol) and chiral ligand (M=Ru, R=i-Pr, Ar=4-MeC 6 h 4 -, 2 μmol) was dissolved in methanol (3 mL), heated and stirred at 0°C for 1 hour. Cool to room temperature, remove the solvent under reduced pressure, and separate by column chromatography (using a silica gel column, eluent: ethyl acetate / petroleum ether = 1 / 5) to obtain 3.21 mg of a dark green solid with a yield of 92%.

[0061] Preparation of 3-benzylmethylamino-1-phenylpropanol from 3-benzylmethylamino-1-propiophenone

[0062]

[0063] Under nitrogen atmosphere, 3-benzylmethylamino-1-propiophenone (0.4mmol), methanol (2.6mL), potassium hydroxide in methanol (0.4mL, 0.08M) and catalyst 1.73mg (TON=400) were added. The reaction system was placed in an autoclave at 25 °C and H 2 (20atm) and stirred for 6 hours. The solvent was removed under reduced pressure, separated by colum...

Embodiment 2

[0065] Synthesis of Hilarochiral Double Reaction Center Ruthenium Catalysts

[0066] Tris(triphenylphosphine)ruthenium dichloride (3.8 mg, 4 μmmol) and chiral ligands (M=Ru, R=s-Bu, Ar=C 6 h 5 -, 2.8 μmmol) was dissolved in ethanol (3 mL), heated and stirred at 30°C for 2 hours. Cool to room temperature, remove the solvent under reduced pressure, and separate by column chromatography (using a silica gel column, eluent: ethyl acetate / petroleum ether = 1 / 5) to obtain 3.31 mg of a dark green solid with a yield of 94.8%.

[0067] Preparation of 3-benzylmethylamino-1-phenylpropanol from 3-benzylmethylamino-1-propiophenone

[0068]

[0069] Under nitrogen atmosphere, 3-benzylmethylamino-1-propiophenone (0.4mmol), ethanol (2.6mL), potassium hydroxide in ethanol (0.4mL, 0.09M) and catalyst 1.715mg (TON=400) were added. The reaction system was placed in an autoclave at 25 °C and H 2 (20atm) and stirred for 12 hours. The solvent was removed under reduced pressure, separated by col...

Embodiment 3

[0071] Synthesis of Hilarochiral Double Reaction Center Ruthenium Catalysts

[0072] Tris(triphenylphosphine)ruthenium dichloride (3.8 mg, 4 μmmol) and chiral ligand (M=Ru, R=Me, Ar=3,5-(CF 3 ) 2 C 6 h 3 -, 2.2 μmmol) was dissolved in toluene (3 mL), heated and stirred at 100°C for 2 hours. Cool to room temperature, remove the solvent under reduced pressure, and separate by column chromatography (using a silica gel column, eluent: ethyl acetate / petroleum ether=1 / 5) to obtain 3.56 mg of a dark green solid with a yield of 96.1%.

[0073] Preparation of 3-benzylmethylamino-1-phenylpropanol from 3-benzylmethylamino-1-propiophenone

[0074]

[0075] Under nitrogen atmosphere, 3-benzylmethylamino-1-propiophenone (0.4mmol), toluene (2.6mL), potassium hydroxide aqueous solution (0.4mL, 0.1M) and catalyst 1.715mg (TON=400) were added. The reaction system was placed in an autoclave at 10 °C and H 2 (20atm) and stirred for 12 hours. The solvent was removed under reduced pressur...

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PUM

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Abstract

The invention discloses a planar chiral double-reactive center ruthenium catalyst, synthesis and an application thereof. The planar chiral double-reactive center ruthenium catalyst provided by the invention not only is simple in synthesis, but also has double reactive centers, and can be used efficiently for asymmetric catalytic hydrogenation of beta-aminoketone compounds; and finally a conversion rate of 100% and an asymmetric induction effect of more than 99.9% can be achieved. The synthesis of the catalyst of the invention is simple in operation, and high in selectivity and yield, and has good atom economy and good industrial application prospects.

Description

technical field [0001] The present invention relates to a ruthenium catalyst and its synthesis and application, in particular to a hemichiral double reaction center ruthenium catalyst and its synthesis method, and its application in the asymmetric hydrogenation of β-amino ketone compounds; it belongs to organic and The field of pharmaceutical synthetic chemistry. Background technique [0002] Chiral amino alcohols are widely used in fine chemicals such as drugs, pesticides, and spices. They are also important precursors for various compounds such as halides, amino compounds, esters, ethers, etc., and can also be synthesized after modification. A variety of chiral ligands are used in catalytic reactions. In recent years, the research on its various synthetic methods is increasing day by day. Among them, the asymmetric hydrogenation of prochiral amino ketones is one of the most important methods for the preparation of chiral amino alcohols. This method has high catalytic ac...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07F17/02C07B41/02C07C215/30C07C213/00C07C217/72C07D307/52
Inventor 张万斌刘德龙王家豪
Owner SHANGHAI JIAO TONG UNIV
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