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A method for palladium-catalyzed asymmetric hydrogenation of chiral 3-trifluoromethyl-3,4-dihydroquinoxalinone

A technology of trifluoromethylquinoxalinone and dihydroquinoxalinone, which is applied in the field of asymmetric hydrogenation synthesis, and achieves the effects of simple and practical reaction operation, convenient preparation and convenient separation

Active Publication Date: 2021-11-02
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, so far, the synthesis of chiral fluorinated dihydroquinoxalinones is still rarely reported.

Method used

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  • A method for palladium-catalyzed asymmetric hydrogenation of chiral 3-trifluoromethyl-3,4-dihydroquinoxalinone
  • A method for palladium-catalyzed asymmetric hydrogenation of chiral 3-trifluoromethyl-3,4-dihydroquinoxalinone
  • A method for palladium-catalyzed asymmetric hydrogenation of chiral 3-trifluoromethyl-3,4-dihydroquinoxalinone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-8

[0033] Condition optimization

[0034] Palladium (0.0025 mmol, 0.85 mg) and chiral ligand (0.003 mmol) were investigated in the reaction flask, and 1 ml of acetone was added after browning, and stirred at room temperature for 1 hour. Then, concentrated in vacuo, 3 ml of the organic solvent was added under nitrogen, and the solution was transferred to a reaction kettle presented with a substrate 1a (27 mg, 0.125 mmol), and hydrogen 600 psi was transferred to 60 ° C for 48 hours. Hydrogen is slowly released, and the direct column chromatography is removed from the solvent to obtain a pure product, alter the type of the organic solvent and the chiral bisphosphine ligand in the reaction, the temperature of the reaction, and the specific structure (Table 1), reaction and matching The body structure is as follows:

[0035]

[0036] The enantiomeric excess of the product was determined by a chromatographic chromatography, which is shown in Table 1.

[0037] Table 1. Asymmetric hydridin...

Embodiment 9-23

[0041] Palladium catalytic asymmetric hydrogenation synthesis of various chirofluoromethyl dihydroquinoxalin 2

[0042] Palladium (1.7 mg, 0.0050 mmol) and (R) -Segphos (3.4 mg, 0.0055 mmmol) were investred in the reaction flask, and 1 ml of acetone was added after nitrogen, and stirred at room temperature for 1 hour. Then, concentrated in vacuo, 3 ml of hexafluoropropyl alcohol was added under nitrogen, and the solution was transferred to a reaction kettle presented with a substrate (0.25 mmol), and hydrogen was transferred to 600 psi, and the reaction was reacted for 48 hours, and hydrogen was slowly released. The type of the reaction substrate is changed, as in Table 2. The pure product was separated from the direct column chromatography after removing the solvent, and the reaction formula was as follows:

[0043]

[0044] Table 2. Asymmetric hydrogenated substrate expansion of trifluorolinolinone

[0045]

[0046] The corresponding products obtained in Examples 9-23 are 2a...

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Abstract

A method for synthesizing chiral 3-trifluoromethyl-3,4-dihydroquinoxalinone by palladium-catalyzed asymmetric hydrogenation, the catalytic system is a chiral bisphosphorus complex of palladium, and the reaction conditions are: temperature: 0- 80°C; solvent: 2,2,2-trifluoroethanol or hexafluoroisopropanol; pressure: 100-1000psi; ratio of substrate to catalyst is 33 / l; metal precursor used: palladium trifluoroacetate; The chiral ligand used: chiral diphosphorus ligand; the preparation method of the catalyst is: stirring the metal precursor of palladium and the chiral diphosphorus ligand in acetone at room temperature, and then vacuum concentrating to obtain the catalyst. The hydrogenation of trifluoromethyl-containing quinoxalinone can give the corresponding chiral trifluoromethyl-containing dihydroquinoxalinone, and its enantiomeric excess can reach 99%. The invention has the advantages of simple and practical operation, high enantioselectivity and good yield, and the reaction has green atom economy and is friendly to the environment.

Description

Technical field [0001] The present invention belongs to the field of asymmetric hydrogenation, and more particularly to a homogeneous system height of the application of palladium, a highly enantiostelective catalytic hydride trifluoromethyl quinoxalinone synthesis chipide-3,4-dihydroquine 喔 喔Method of plymonzone. Background technique [0002] Chiral dihydroquinolinone is a core architecture of many pesticides, pharmaceutical intermediates, and natural products. Therefore, the synthesis and biological activity of such compounds have caused extensive attention to organic chemists and pharmacies. Hereinafter (formula 1) is a structural unit containing pharmaceutically active molecules containing chiral dihydroquinoxalinone: [0003] [0004] Given the importance of chiral dihydroquinoxalin and its derivatives in the field of drug and synthetic chemistry, chemists have developed some methods to synthesize such compounds. However, it is usually synthesized by equivalent amino acid ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D241/44C07D241/38
CPCC07D241/38C07D241/44
Inventor 陈木旺周永贵孙蕾
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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