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A kind of chiral double reaction center ruthenium catalyst and its synthesis and application

A ruthenium catalyst and double-reaction technology, applied in the face-chiral double-reaction center ruthenium catalyst and its synthesis, the application of asymmetric hydrogenation of β-amino ketone compounds, ruthenium catalyst and its synthesis and application field, can solve the problem of catalyst Ligand synthesis is complicated, stable storage is not possible, and the cost of metal rhodium is high, so as to achieve good industrial application prospects, convenient storage and use, and good catalytic effect

Active Publication Date: 2016-12-28
SHANGHAI JIAOTONG 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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  • A kind of chiral double reaction center ruthenium catalyst and its synthesis and application
  • A kind of chiral double reaction center ruthenium catalyst and its synthesis and application
  • A kind of chiral double reaction center ruthenium catalyst and its synthesis and application

Examples

Experimental program
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Effect test

Embodiment 1

[0058] Synthesis of Hilarochiral Double Reaction Center Ruthenium Catalysts

[0059] 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%.

[0060] Preparation of 3-benzylmethylamino-1-phenylpropanol from 3-benzylmethylamino-1-propiophenone

[0061]

[0062] 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

[0064] Synthesis of Hilarochiral Double Reaction Center Ruthenium Catalysts

[0065] 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%.

[0066] Preparation of 3-benzylmethylamino-1-phenylpropanol from 3-benzylmethylamino-1-propiophenone

[0067]

[0068] 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

[0070] Synthesis of Hilarochiral Double Reaction Center Ruthenium Catalysts

[0071] 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%.

[0072] Preparation of 3-benzylmethylamino-1-phenylpropanol from 3-benzylmethylamino-1-propiophenone

[0073]

[0074] 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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Abstract

The invention discloses a chiral double reaction center ruthenium catalyst as well as its synthesis and application. The chiral double-reaction center ruthenium catalyst provided by the present invention is not only easy to synthesize, but also the double-reaction center ruthenium catalyst it has can be efficiently applied to the asymmetric catalytic hydrogenation of β-aminoketone compounds; finally, 100% conversion can be obtained rate and more than 99.9% asymmetry induction effect. The synthesis operation of the catalyst described in the invention is simple and convenient, the selectivity and yield are high, the catalyst has good atom economy and good industrial application prospect.

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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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/24C07F17/02C07B41/02C07C215/30C07C213/00C07C217/72C07D307/52
Inventor 张万斌刘德龙王家豪
Owner SHANGHAI JIAOTONG UNIV
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