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Synthetic method of marine natural product Puupehenol

A technology of natural products and synthetic methods, applied in the production of bulk chemicals, organic chemistry, etc., can solve the problems of low yield, long synthetic route, poor stereoselectivity, etc., and achieve good product selectivity, high total yield, and reaction The effect of fewer steps

Inactive Publication Date: 2017-04-26
HARBIN INST OF TECH AT WEIHAI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, there are few reports on the synthesis methods of Puupehenol, and most of them have disadvantages such as long synthetic routes, expensive starting materials or reagents, poor stereoselection of methyl C-8 in the reaction process, and low yields.
People such as Alejandro F. Barrero reported in 1997, completed the synthetic research of Puupehenol ( Tetrahedron , 1999, 55,(52): 15181–15208), but this method has extremely low yield and poor stereoselectivity, and is not suitable for industrial production

Method used

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  • Synthetic method of marine natural product Puupehenol
  • Synthetic method of marine natural product Puupehenol

Examples

Experimental program
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Effect test

Embodiment 1

[0021] Example 1: Iodo 1,2,4-trimethoxybenzene (3, see figure 1 )Synthesis

[0022] Take 1.68 g (2, 10.0 mmol) of 1,2,4-trimethoxybenzene and dissolve it in 25 ml of anhydrous acetonitrile, add NIS (10.0 mmol), stir and react at room temperature for 2 hours, and TLC detects that the reaction is complete. Add 30 ml of water, extract with ethyl acetate (30mL x 3), combine the organic phases, wash with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and purify by column chromatography to give white solid iodo 1,2,4- Trimethoxybenzene 2.90 grams, yield is 99%.

Embodiment 2

[0023] Embodiment 2: (+) clary perilla hydrazone (5, see figure 1 )Synthesis

[0024] Take 2.38 g (+) sclarealdehyde (4, 10.0 mmol) and dissolve it in 30 ml of anhydrous methanol, add 1.86 g (10.0 mmol) of p-toluenesulfonyl hydrazide, stir and react at room temperature for 3 hours, and TLC detects that the reaction is complete. Concentrate to obtain white solid (+) sulfonyl hydrazone.

Embodiment 3

[0025] Embodiment 3: the basic framework of Puupehenol (6, see figure 1 )Synthesis

[0026] Take (+) 407 mg (5, 1.0 mmol) of clarylar sulfonylhydrazone and dissolve it in 4 ml of anhydrous tetrahydrofuran, add 23 mg (0.02 mmol) of tetrakistriphenylphosphine palladium and 622 mg (4.5 mmol) of potassium carbonate repeatedly Inflate and exhaust argon three times to exhaust the air. Another 294 mg iodo-1,2,4-trimethoxybenzene (3, see figure 1 ) was dissolved in 2 ml of anhydrous tetrahydrofuran, slowly added dropwise to the above reaction system, and the temperature was raised to 110 o C, the reaction was stirred for 10 hours, and the reaction was detected by TLC. Add 30 ml of water to the reaction system, extract with ethyl acetate (10 mL x 3), combine the organic phases, wash with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and purify by column chromatography to give a light yellow oil 315 mg, the yield was 81%.

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Abstract

The invention relates to a synthetic method of a marine natural product Puupehenol, and belongs to the field of chemical synthesis. The synthetic method comprises the steps: taking (+) aromatic perillaldehyde and hydroxyquinol as starting raw materials, firstly, utilizing (+) aromatic perillaldehyde and p-toluenesulfonhydrazide to form (+) aromatic perillasulfonyl hydrazone, then carrying out palladium-catalyzed cascade Carving migration insertion and intramolecular cyclization reaction of iodine substituted 1,2,4-trimethoxybenzene and (+) aromatic perillasulfonyl hydrazone in an alkali environment to obtain a marine natural product Puupehenol skeleton; and then carrying out hydroxy reduction and double-bond isomerization of a bicyclic sesquiterpanes part of the Puupehenol skeleton, and carrying out oxidation, reduction, cyclization and protection group removal to obtain the final target product Puupehenol. The synthetic method has the advantages of fewer reaction steps, simple operation, and good product selectivity, and is suitable for industrialized production.

Description

technical field [0001] The invention relates to a method for synthesizing Puupehenol, a marine natural product. Background technique [0002] The marine natural product Puupehenol belongs to the Puupehenone class of marine natural products. The marine natural product Puupehenone was first obtained from deep-sea sponges in 1979 Heteronema and Hyrtiose ubnamma The first separation and extraction in ( Pure and Applied Chemistry , 1979, 51(9): 1893-1900). Then in 1986, Shigeo Kohmoto et al. from the deep sea sponge Strongylophorai Hartmani It was separated and extracted again, and its structure was identified by mass spectrometry, infrared and nuclear magnetic resonance techniques, and it was found that it is a cytotoxic sesquiterpene-methylidene quinone ( The Journal of Organic Chemistry , 1993, 58(24): 6565–6569), the structure is as figure 1 . Its derivatives are important marine metabolites exhibiting various biological activities including cytotoxicity, antivira...

Claims

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Application Information

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IPC IPC(8): C07D311/78
CPCY02P20/55C07D311/78
Inventor 吴彦超王洪双李惠静
Owner HARBIN INST OF TECH AT WEIHAI
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