Synthesis method of chiral 2-hydroxy-1, 4-dicarbonyl compound and pantoic acid lactone

A kind of pantolactone, monohydrate technology, applied in the field of synthetic products, can solve problems such as no systematic report

Active Publication Date: 2020-10-30
LANZHOU UNIVERSITY +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The method for studying the asymmetric Aldol reaction between aliphatic aldehyde and acyl formaldehyde monohydrate has not been systematically reported yet, but is scattered in various articles [Kano, T.; Maruoka K.Angew.Chem.Int.Ed.2007, 46, 1738–1740]; [Kano, T.; Maruoka, K. Chem. Eur. J. 2009, 15, 6678–6687]; [Yan X.; Feng, X.M. Synlett. Both use small molecule secondary amine catalysts

Method used

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  • Synthesis method of chiral 2-hydroxy-1, 4-dicarbonyl compound and pantoic acid lactone
  • Synthesis method of chiral 2-hydroxy-1, 4-dicarbonyl compound and pantoic acid lactone
  • Synthesis method of chiral 2-hydroxy-1, 4-dicarbonyl compound and pantoic acid lactone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023]

[0024] Add accurately weighed tetrapeptide catalyst ent-TP (0.025mmol) and 1.0mL dichloromethane into a 5mL round bottom flask, add isobutyraldehyde (92μL, 1.0mmol) while stirring in an ice-water bath, and then add glyoxylic acid Ethyl ester (50% toluene solution, 0.1 mL, 0.5 mmol), the reaction was returned to room temperature and stirred, detected by TLC, and the progress of the reaction was judged by color development with 2,4-dinitrophenylhydrazine. After the reaction, add 3-4 drops of saturated ammonium chloride solution, extract with ethyl acetate (10mL×3), wash with a small amount of saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and purify the residual oil by column chromatography. The product (S)-P-1 is obtained.

[0025] Table 1. The results of tetrapeptide catalysts ent-TP-1~ent-TP-6 catalyzing the asymmetric Aldol reaction between isobutyraldehyde and ethyl glyoxylate

[0026]

[0027] a Isolated yield. b The...

Embodiment 2

[0029]

[0030] Add accurately weighed tetrapeptide catalyst ent-TP-2 (0.025mmol, 10mg) and 1.0mL solvent into a 5mL round bottom flask, add isobutyraldehyde (92μL, 1.0mmol) while stirring in an ice-water bath, and then add ethyl Ethyl alkydate (50% toluene solution, 0.1 mL, 0.5 mmol), the reaction was returned to room temperature and stirred, detected by TLC, and the progress of the reaction was judged by color development with 2,4-dinitrophenylhydrazine. After the reaction, add 3-4 drops of saturated ammonium chloride solution to quench the reaction, extract with ethyl acetate (10mL×3), wash with a small amount of saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and purify the residue by column chromatography. As an oil, (S)-P-1 was obtained.

[0031] Table 3. Effect of solvent on the asymmetric Aldol reaction of isobutyraldehyde and ethyl glyoxylate catalyzed by tetrapeptide ent-TP-2

[0032]

[0033] a Isolated yield. b The e...

Embodiment 3

[0035]

[0036] Add accurately weighed tetrapeptide catalyst TP (0.025mmol) and 1.0mL acetonitrile into a 5mL round bottom flask, add isobutyraldehyde (92μL, 1.0mmol) while stirring in an ice-water bath, and then add ethyl glyoxylate (50 % toluene solution, 0.1mL, 0.5mmol), the reaction was returned to room temperature and stirred, detected by TLC, and the progress of the reaction was judged by color development with 2,4-dinitrophenylhydrazine. After the reaction, add 3-4 drops of saturated ammonium chloride solution, extract with ethyl acetate (10mL×3), wash with a small amount of saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and purify the residual oil by column chromatography. The reaction product (R)-P-1 was obtained.

[0037] Table 2. Tetrapeptides TP-1~TP-6 catalyze the asymmetric Aldol reaction of isobutyraldehyde and ethyl glyoxylate

[0038]

[0039] a Isolated yield. b The ee value was determined from the benzoate es...

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Abstract

The invention discloses a chiral 2-hydroxy-1, 4-dicarbonyl compound synthesized by catalyzing asymmetric Aldol reaction of fatty aldehyde and glyoxylate or fatty aldehyde and acylformaldehyde monohydrate by taking tetrapeptide TP or an enantiomer ent-TP thereof as a chiral catalyst, and application of a synthetic product. The method for synthesizing the chiral 2-hydroxy-1, 4-dicarbonyl compound through the asymmetric Aldol reaction is shown as a formula 1 and a formula 2. The asymmetric Aldol reaction of fatty aldehyde and glyoxylate or fatty aldehyde and acylformaldehyde monohydrate is catalyzed to synthesize the optically active 2-hydroxy-1, 4-dicarbonyl compound, then the optically active pantoic acid lactone can be further synthesized, and the method has advantages of mild reaction conditions, easy operation, low catalyst consumption, high yield and the like, and can synthesize the 2-hydroxy-1, 4-dicarbonyl compounds with two configurations by using tetrapeptide and the enantiomerthereof.

Description

technical field [0001] The invention relates to a kind of asymmetric Aldol reaction of fatty aldehyde and glyoxylate or fatty aldehyde and acyl formaldehyde monohydrate catalyzed by a chiral catalyst of tetrapeptide or its enantiomer to synthesize chiral 2-hydroxyl-1 , 4-dicarbonyl compounds, and uses of synthetic products. Background technique [0002] Optically active compounds are ubiquitous in nature and play an irreplaceable role in the life activities of cells and organisms. Many drugs are optically active compounds, and chirality is an important element of drugs. The use of chiral catalysts to catalyze asymmetric reactions is the most economical and green method for the synthesis of chiral compounds. Asymmetric catalysis includes three fields, namely, chiral ligand-metal complex catalysts, organic small molecule catalysts and biological enzyme catalyzed reactions. Due to its green and good economic performance, biological enzyme catalysis has always been a hot rese...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B53/00C07D307/33C07C67/343C07C69/67C07C45/72C07C49/86C07C49/258C07D307/46C07D333/22
CPCC07B53/00C07D307/33C07C67/343C07C45/72C07D307/46C07D333/22C07B2200/07C07C2601/08C07C2601/14C07C69/716C07C49/86C07C49/258C07C2603/24
Inventor 达朝山杜智宏陶宝秀秦文娟袁梦白彦兵林行张连春殷杭华姜伟林余建新刘学愚金文究
Owner LANZHOU UNIVERSITY
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