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Method for asymmetrically synthesizing glabridin with optical purity under catalysis of ruthenium compound

A technology of optical purity and ruthenium complex, applied in organic chemistry methods, organic chemistry, bulk chemical production, etc., to achieve the effects of easy product purification, high stereoselectivity, and simple operation

Active Publication Date: 2018-08-24
烟台六谛医药科技有限公司 +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0014] In summary, up to now, the artificial synthesis methods of glabridin reported in chemical literature and patents are the preparation methods of racemic glabridin, and there has not been a method capable of synthesizing optically pure glabridin. Due to the increase in demand for glabridin, the chemical synthesis of glabridin with optical purity in the (R)-configuration has become an urgent need

Method used

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  • Method for asymmetrically synthesizing glabridin with optical purity under catalysis of ruthenium compound
  • Method for asymmetrically synthesizing glabridin with optical purity under catalysis of ruthenium compound
  • Method for asymmetrically synthesizing glabridin with optical purity under catalysis of ruthenium compound

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Embodiment 1

[0046] A method for asymmetrically synthesizing glabridin with optical purity, comprising the steps of:

[0047] 1) Synthesis of compound II-a(3R,4R)-3-(2,4-dimethoxyphenyl)-8,8-dimethyl-3,4-dihydro-2H,8H-pyrano[2,3-f]chromen-4 -ol, the chemical equation is:

[0048]

[0049] The specific experimental steps and operations are as follows: at room temperature, 1.25 mmol of dichloro(p-methylisopropylphenyl) ruthenium (II) dimer (CAS number: 52462-29-0, provided by Shanghai Neutron Star Chemical Technology Co., Ltd. company) and 2.5 mmol (R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine [(R,R)-TsDPEN, CAS#144222-34-4, supplied by TCI Purchased from Shanghai branch] were added to 150mL of stirred ethyl acetate in sequence; then, the triethylamine / formic acid buffered proton system that was previously mixed with 60mL of triethylamine and 20mL of formic acid and cooled to room temperature was added. The entire mixed system was stirred at room temperature for 30 minutes to ...

Embodiment 2

[0069] A method for asymmetrically synthesizing glabridin with optical purity, comprising the steps of:

[0070] 1) synthesis of compound II-b,

[0071] 4-((3R,4R)-4-hydroxy-8,8-dimethyl-3,4-dihydro-2H,8H-pyrano[2,3-f]chromen-3-yl)-1,3-phenylene diacetate :

[0072] The chemical formula is:

[0073]

[0074] The experimental steps and operations are as follows: at room temperature (25° C.), 2.50 mmol of dichloro(p-methylisopropylphenyl) ruthenium (II) dimer (CAS number: 52462-29-0) and 5.0 mmol ( R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine [(R,R)-TsDPEN, CAS#144222-34-4] was sequentially added to 300 mL of stirred ethyl acetate Then, add the triethylamine / propionic acid buffered proton system which was previously mixed with 120mL triethylamine and 40mL propionic acid and cooled to room temperature. The entire mixed system was stirred at room temperature for 30 minutes to form a uniform LC solution of the active metal catalyst; set aside. Install a mechanical...

Embodiment 3

[0091] A method for asymmetrically synthesizing glabridin with optical purity, comprising the steps of:

[0092] 1) synthesis of compound II-c,

[0093] 4-((3R,4R)-4-hydroxy-8,8-dimethyl-3,4-dihydro-2H,8H-pyrano[2,3-f]chromen-3-yl)-1,3-phenylene dimethylsulfonate :

[0094] The chemical formula is:

[0095]

[0096] The experimental steps and operations are as follows: at room temperature (25°C), mix 0.05 mmol of dichloro(p-methylisopropylphenyl) ruthenium (II) dimer (CAS number: 52462-29-0) and 0.1 mmol ( R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine [(R,R)-TsDPEN, CAS#144222-34-4] was sequentially added to 200 mL of stirred ethyl acetate In; then add the diisopropylethylamine / formic acid buffer proton system that was previously mixed with 96mL diisopropylethylamine and 32mL formic acid and cooled to room temperature. The entire mixed system was stirred at room temperature for 30 minutes to form a uniform LC solution of the active metal catalyst; set aside. I...

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Abstract

The invention relates to a method for asymmetrically synthesizing glabridin with optical purity under catalysis of a ruthenium compound. The method comprises the following steps: 1) taking isoflavoneprotected by a protection group as a raw material and carrying out dynamic kinetic asymmetric hydrogen transfer reaction under the catalysis effect of a ruthenium trichloride compound and the action of an acid-alkali buffering system to obtain chiral isoflavol with an absolute configuration being (3R, 4R); 2) removing hydroxyl of the chiral isoflavol under the action of triethylsilane and trifluoroacetic acid to obtain a product with an absolute configuration being (R); 3) removing a protection group of the product with the configuration being (R) in step 2) under an acidic or alkaline condition to obtain the glabridin with the configuration (R) and the optical purity. The method provided by the invention can be used for synthesizing the glabridin with the optical purity in a high-yield and high-stereoselectivity manner; the obtained product is completely the same as that of the glabridin extracted from glycyrrhiza glabra and can be used for replacing the glabridin derived from naturalplants to be industrially applied.

Description

technical field [0001] The invention relates to a method for synthesizing glabridin, in particular to a method for synthesizing optically pure glabridin, which belongs to the technical field of organic synthesis. Background technique [0002] Glabridin is one of the main flavonoids in Glycyrrhiza glabra, which was initially isolated and identified from the root of licorice (literature: Saitoh, T.; Kinoshita, T.; Shibata, S.; Chem.Pharma.Bull.1976,24,752-755), also rich in this composition in the licorice glabra planted in China. Glabridin has a strong anti-free radical oxidation effect in the cytochrome P450 / NADPH oxidation system, which can significantly inhibit the free radicals produced in the metabolic process in the body, and prevent oxidation-sensitive biological macromolecules (low-density lipoprotein LDL , DNA) and cell walls are oxidized and damaged by free radicals, which can prevent certain pathological changes related to free radical oxidation, such as atheroscl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D493/04
CPCC07B2200/07C07D493/04Y02P20/55
Inventor 杨家德曲文超范玉龙陈婷婷李伟钮坚
Owner 烟台六谛医药科技有限公司
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