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Synthetic method of alpha-amino acid with photolytic activity

A synthetic method and photoactive technology, which are applied in the field of α-amino acid synthesis, can solve the problems of waste of raw materials, impact on application, limitation of chiral α-amino acid species, etc.

Inactive Publication Date: 2012-11-07
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The resolution method uses the racemic α-amino acid as the raw material, and obtains one configuration of the amino acid after chiral resolution. This method has a maximum yield of 50%, and the other configuration is discarded, resulting in the loss of raw materials waste
For fermentation and enzyme-catalyzed methods, the types of chiral α-amino acids produced are limited due to the specificity of microorganisms and enzymes
The most direct way to prepare chiral α-amino acids in organic synthesis is the catalytic hydrogenation of imines, but the introduction of metals and hydrogen, high temperature, high pressure and other conditions affect the industrial application of imine hydrogenation reactions

Method used

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  • Synthetic method of alpha-amino acid with photolytic activity
  • Synthetic method of alpha-amino acid with photolytic activity
  • Synthetic method of alpha-amino acid with photolytic activity

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0069] Example 1 (R)-2-amino-4-phenyl-butyric acid-3-ethyl-3-pentyl ester (see structural formula 12-a):

[0070]

[0071] n Bu is n-butyl; Et is ethyl; Cat represents catalyst

[0072] Under the protection of nitrogen, add 1-phenyl-3-oxobutanoic acid-3-ethyl-3-pentyl ester (0.50mmol, 0.138g) of the structural formula 5-a described in the above reaction formula to the reactor successively , o-chlorobenzylamine (0.50 mmol, 0.071 g) and 1.0 mL of benzene. Put the reactor into an oil bath at 70° C. After reacting for 12 hours, take the reactor out from the oil bath and place it at room temperature, and add the chiral base (0.05 mmol, 0.018g) and 9.0mL benzene, adjust the temperature of the oil bath to 50°C. After 24 hours, the heating was stopped, and the solvent benzene was spin-dried to obtain the crude transamination product of the structural formula 11-a described in the above reaction formula. The conversion rate was 100% as determined by NMR, and the next step reactio...

Embodiment 2

[0077] Embodiment 2 (R)-2-amino-4-phenylbutyric acid ethyl ester (see structural formula 12-b):

[0078]

[0079] Et is ethyl; Cat is catalyst

[0080] Under the protection of nitrogen, add 1-phenyl-3-oxobutanoic acid ethyl (0.20mmol, 0.041g), p-fluorobenzylamine (0.50mmol , 0.063g) and 1.0mL toluene. Put the reactor into an oil bath at 25° C. After reacting for 2 hours, take the reactor out from the oil bath and place it at room temperature, and add the chiral base (0.02 mmol, 0.006g) and 1.0mL toluene, adjust the temperature of the oil bath to 100°C. Heating was stopped after 15 hours, and the crude product of transamination with the structural formula 11-b described in the above reaction formula was obtained after spin-drying toluene. The conversion rate was 100% as determined by NMR, and the next step reaction was directly performed without further purification.

[0081] The transamination crude product obtained by the above reaction with the structural formula 11-b ...

Embodiment 3

[0085] Embodiment 3 (R)-2-amino-4-phenylbutyric acid tert-butyl ester (see structural formula 12-c):

[0086]

[0087] t Bu is tert-butyl; Cat represents catalyst

[0088] Under the protection of nitrogen, add 1-phenyl-3-oxobutanoic acid tert-butyl (0.20mmol, 0.047g) of 1-phenyl-3-oxobutanoic acid tert-butyl (0.20mmol, 0.047g), o-chlorobenzylamine (0.20 mmol, 0.028g) and 0.5mL toluene. Put the reactor into an oil bath at 100° C. After reacting for 12 hours, take the reactor out from the oil bath and place it at room temperature, and add the chiral base (0.02 mmol, 0.007g) and 1.5mL toluene, the temperature of the oil bath was adjusted to 40°C. Heating was stopped after 12 hours, and the crude product of transamination with the structural formula 11-c described in the above reaction formula was obtained after spin-drying toluene. The conversion rate was 100% as determined by NMR, and the next step reaction was directly carried out without further purification.

[0089] T...

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PUM

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Abstract

The invention belongs to an amino acid compound, especially to a synthetic method of alpha-amino acid with photolytic activity by asymmetric biomimetic transamination. The synthetic method comprises the following steps of: using alpha-keto ester and benzylamine as raw materials, using cinchona alkaloid derived chiral base A or chiral base B as a catalyst to catalyze alpha-keto ester with different structures by one kettle way to carry out asymmetric transamination, carrying out post-treatment such as hydrolysis, extraction, column chromatography and the like, synthesizing to prepare alpha-amino ester with photolytic activity, and finally carrying out hydrolysis to obtain (chiral)alpha-amino acid with photolytic activity. Enantiomeric excess value (ee value) can be as high as 92%.

Description

technical field [0001] The invention belongs to amino acid compounds, in particular to a synthetic method of asymmetric biomimetic transamination reaction-photoactive α-amino acid. Background technique [0002] The photoactive α-amino acid is one of the most important substances in organisms and organic synthesis. They are a basic structural unit of protein and a key element to maintain the life of organisms. In organic synthesis, they are a class of synthons in the total synthesis of drug molecules, and they are also important structural skeletons that constitute chiral ligands. [0003] At present, most of the α-amino acids are produced in industry by resolution method, fermentation method and bio-enzyme catalysis method. The resolution method uses the racemic α-amino acid as the raw material, and obtains one configuration of the amino acid after chiral resolution. This method has a maximum yield of 50%, and the other configuration is discarded, resulting in the loss of ...

Claims

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Application Information

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IPC IPC(8): C07C227/32C07C229/36C07C229/08C07C229/22C07C229/30
Inventor 史一安肖晓谢颖苏寸香刘懋
Owner INST OF CHEM CHINESE ACAD OF SCI
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