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Method for synthesizing derivatives of chiral tetrahydroquinoline by catalyzing asymmetric hydrosilylation with iridium

A derivative, asymmetric technology, used in chemical instruments and methods, chemical/physical processes, physical/chemical process catalysts, etc., can solve problems such as high pressure, achieve complete reaction, high reactivity and enantioselectivity, To achieve the effect of chiral value-added

Inactive Publication Date: 2010-09-29
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

However, due to the use of dangerous goods such as hydrogen and the excessive pressure of hydrogen, the industrial application is limited to a certain extent. Therefore, it is very urgent to further develop and improve this technology.

Method used

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  • Method for synthesizing derivatives of chiral tetrahydroquinoline by catalyzing asymmetric hydrosilylation with iridium
  • Method for synthesizing derivatives of chiral tetrahydroquinoline by catalyzing asymmetric hydrosilylation with iridium
  • Method for synthesizing derivatives of chiral tetrahydroquinoline by catalyzing asymmetric hydrosilylation with iridium

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Experimental program
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Embodiment 1

[0026] Embodiment 1: optimization of conditions

[0027] Add iridium precursor (1.7mg, 0.0025mmol) and chiral ligand (0.0055mmol) into the reaction bottle, add 1ml of tetrahydrofuran after nitrogen replacement, and stir at room temperature for 10 minutes. Then elemental iodine (6.4mg, 0.025mmol) was added and stirred at room temperature for 10 minutes. Afterwards, substrate 1a (37mg, 0.25mmol), water (9mg, 0.5mmol) and triethylsilylhydrogen (174mg, 1.50mmol) were added, and finally 2ml of tetrahydrofuran was added, and the reaction was stirred at room temperature for 24 hours. The enantiomeric excess of the product was determined by chiral liquid chromatography, see Table 1. The reaction formula and ligand structure are as follows:

[0028]

[0029] Table 1. Optimization of conditions for iridium-catalyzed asymmetric hydrosilylation of 2-methylquinoline 1a

[0030] serial number

Embodiment 2

[0031] Example 2: Synthesis of Tetrahydroquinoline Derivatives 2 by Iridium-Catalyzed Asymmetric Hydrosilylation

[0032] Add iridium metal precursor (1.7mg, 0.0025mmol) and chiral ligand (3.4mg, 0.0055mmol) into the reaction bottle, add 1ml of tetrahydrofuran after nitrogen replacement, and stir at room temperature for 10 minutes. Then elemental iodine (6.4mg, 0.025mmol) was added and stirred at room temperature for 10 minutes. Afterwards, add substrate 1 (0.25mmol), water (9mg, 0.5mmol) and triethylsilylhydrogen (174mg, 1.50mmol), and finally add 2 milliliters of tetrahydrofuran, stir at room temperature and detect the reaction by TLC, stop stirring when the reaction ends . The reaction time is 24-72 hours, and the enantiomeric excess of the product is determined by chiral liquid chromatography, as shown in Table 2, and the reaction formula is as follows:

[0033]

[0034] Table 2. Iridium-catalyzed asymmetric hydrosilylation synthesis of various chiral tetrahydroquinol...

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Abstract

The invention provides a method for synthesizing derivatives of chiral tetrahydroquinoline by catalyzing asymmetric hydrosilylation with iridium. In the method, a used catalytic system is a chiral duplex phosphorus complex generated in situ. The reaction can be performed under the following conditions: a room temperature; a tetrahydrofuran solvent; a chlorizated cyclooctadiene iridium metallic precursor; and a chiral duplex phosphorus ligand chiral ligand. The method for preparing the catalyst comprises the following steps of: stirring the metallic precursor of iridium and the chiral duplex phosphorus ligand in the tetrahydrofuran at room temperature, adding the simple substance of iodine, stirring the mixture, and finally adding quinoline substrates, triethyl silicon hydrogen and water. By the hydrosilylation of quinoline, the corresponding derivatives of chiral tetrahydroquinoline are obtained, and the enantiomeric excess of the derivatives reaches 93 percent. The method has the advantages of easy and practical operation, readily available raw materials, high antipodal selectivity, high yield, no use of dangerous articles such as hydrogen gas and the like, safety and reliability; in addition, the reaction is environment-friendly.

Description

technical field [0001] The invention relates to a method for synthesizing chiral tetrahydroquinoline derivatives by iridium-catalyzed asymmetric hydrosilylation. Background technique [0002] 1,2,3,4-Tetrahydroquinoline and its derivatives are not only a class of important organic synthesis intermediates and compounds with physiological activity, but also the structural unit of many quinoline alkaloids, so it has attracted widespread attention focus on. For example, the compound 6-fluoro-2-methyl-1,2,3,4-tetrahydroquinoline is an important intermediate of the antibacterial agent Flumequine, and the activity of the (S)-configuration is higher than that of the (R)-configuration. The only way to obtain individual enantiomers is by resolution. [0003] Formula 1 [0004] In recent years, dozens of tetrahydroquinoline alkaloids have been extracted from a plant in South America (Figure 1). Through experiments, it was discovered that this type of compound has the effect of tr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D215/06C07D215/20C07D215/14C07D405/06B01J31/24
Inventor 周永贵王大伟王躲生
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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