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Synthetic method of marine natural product namely (R, Z)-24-methyl-25-carbon-16-butylene-2,4-diyne-1,6-diol and enantiomer thereof

A technology of natural products and synthetic methods, applied in asymmetric synthesis, organic chemical methods, chemical instruments and methods, etc., to achieve the effects of good product stereoselectivity, shortened reaction routes, and increased yields

Active Publication Date: 2015-07-15
河南源博新材料有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But so far, there is no literature report using asymmetric catalysis to synthesize such marine natural products. Therefore, the present invention uses the asymmetric addition of trimethylsilylacetylene and enal to efficiently prepare marine natural products (R, Z)- 24-Methyl-pentacosa-16-butene-2,4-diyne-1,6-diol and its enantiomers

Method used

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  • Synthetic method of marine natural product namely (R, Z)-24-methyl-25-carbon-16-butylene-2,4-diyne-1,6-diol and enantiomer thereof
  • Synthetic method of marine natural product namely (R, Z)-24-methyl-25-carbon-16-butylene-2,4-diyne-1,6-diol and enantiomer thereof
  • Synthetic method of marine natural product namely (R, Z)-24-methyl-25-carbon-16-butylene-2,4-diyne-1,6-diol and enantiomer thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0024] Example 1 Preparation of dodec-2-en-1-ol

[0025] Under nitrogen protection, hexamethylphosphoric triamide (42 mL) and anhydrous tetrahydrofuran (150 mL) were added into a 500 mL Shrek bottle equipped with electromagnetic stirring. After stirring evenly, add propynyl alcohol (5.61g, 100mmol.), stir the mixture and cool it down to -78°C, then slowly add n-butyllithium (80mL of 2.5M solution in hexane), and raise the temperature to - Stir at 30°C for 90 minutes. Subsequently, 1-bromononane (22.8 g, 110 mmol) was slowly added dropwise, and the reaction was stirred for 12 h, during which time it was allowed to warm to room temperature. After the reaction was completed, deionized water (30 mL) was added to quench the reaction. The aqueous phase was extracted with ethyl acetate (50 mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. Finally, purification by silica gel column chroma...

Embodiment 2

[0026] Example 2 Preparation of 2-(dodeca-11-ynyl-1-oxygen)tetrahydro-2H-pyran

[0027] At zero temperature, add 1,3-propylenediamine (125mL) and sodium hydrogen (10.0g, 250mmol, 60% in mineral oil) into a 500mL three-necked flask equipped with mechanical stirring, and stir for 30 minutes, the system rises Temperature to 70°C, after stirring for 60 minutes. After the temperature of the system dropped to room temperature, dodec-2-en-1-ol (9.1 g, 50 mmol) was slowly added in batches. The reaction was continued to stir overnight at 55°C. After the reaction was completed, deionized water (10 mL) was added to quench the reaction. The aqueous phase was back-extracted with ethyl acetate (50mL x 3), the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product, which was directly subjected to the next reaction. In a 200m three-necked flask equipped with electromagnetic stirring, add the crude product, dihydr...

Embodiment 3

[0028] Example 3 Preparation of 2-((19-methyleicos-11-yn-1-yl)oxy)tetrahydro-2H-pyran

[0029] Under nitrogen protection, hexamethylphosphoric triamide (3.5 mL) and anhydrous tetrahydrofuran (30 mL) were added into a 100 m Shrek bottle equipped with electromagnetic stirring. After stirring evenly, add 2-(dodeca-11-ynyl-1-oxy)tetrahydro-2H-pyran (1.3g, 5mmol.), stir the mixture and cool it down to -78°C, then slowly add n Butyllithium (4.0mL of 2.5M solution in hexane, 10mmol), after the dropwise addition was completed, the temperature was raised to -30°C and stirred for 90 minutes. Then 1-iodo-7-methyloctane (1.9 g, 7.5 mmol) was slowly added dropwise and the reaction was stirred for 12 h, during which time it was allowed to warm to room temperature. After the reaction was completed, deionized water (30 mL) was added to quench the reaction. The aqueous phase was extracted with ethyl acetate (50 mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and...

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Abstract

The invention relates to a synthetic method of a marine natural product namely (R, Z)-24-methyl-25-carbon-16-butylene-2,4-diyne-1,6-diol and an enantiomer thereof, and belongs to the field of chemical synthesis. The synthetic method comprises the following steps: firstly, preparing long chain alkyl iodide by using a series of simple reactions including bromination, oxidation, esterification, reduction and the like; and then, performing multiple steps of reactions including coupling, dislocation, oxidation, selective reduction, asymmetric alkynylation addition, esterification, hydrolysis and the like by taking propargyl alcohol and the long chain alkyl iodide as starting materials to synthesize the marine natural product namely (R, Z)-24-methyl-25-carbon-16-butylene-2,4-diyne-1,6-diol and the enantiomer thereof, wherein the key step is that trimethylsilylacetylene and alkynal are subjected to asymmetric addition reaction to generate alkynol segments with high optical purity by one step. The synthetic method provided by the invention reports the synthesis of the natural product of the type for the first time, and has the characteristics of simple and convenient steps, relatively high total yield, good product stereoselectivity and the like, and the optical purity of each of the two types of synthesized products is more than 99%ee.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, in particular to a marine natural product (R, Z)-24-methyl-pentacosa-16-butene-2,4-diyne-1,6-diol and its Synthetic methods of enantiomers. Background technique [0002] At present, with the development of science and technology, marine natural products have been widely concerned by scientists at home and abroad due to their unique structures and physiological activities (Nat.Prod.Rep.2013,30,237-323), and (R,Z)-24-methyl -Pentacosa-16-butene-2,4-diyne-1,6-diol is a new type of marine natural product. Studies have shown that this natural product has unique effects in anti-tumor and other aspects (Tetrahedron Lett. 2000, 41, 9271-9276.). However, there is a chiral carbon atom in the structure of the natural product, so it has a pair of enantiomers, but because a pair of enantiomers often have a large difference in biological activity, the R type has a sedative effect, and the S type has a sedat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C33/048C07C29/34C07B53/00
CPCY02P20/55
Inventor 郑冰刘飞鹏钟江春边庆花李硕宁刘世阔李敏言
Owner 河南源博新材料有限公司
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