Synthesis method for marine natural product Puupehenone

A natural product and synthetic method technology, applied in organic chemistry and other fields, can solve the problems of long synthetic route, low yield, poor stereoselectivity, etc., and achieve the effect of less reaction steps, high total yield and good product selectivity

Active Publication Date: 2016-06-08
威海惠安康生物科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] At present, there are few reports on the synthesis methods of Puupehenone, and most of them have disadvantages such as long synthetic routes, expensive starting materials or reagents, poor stereoselectivity of methyl C-8 in the reaction process, and low yields.
As reported by AlejandroF.Barrero et al. in 1997

Method used

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  • Synthesis method for marine natural product Puupehenone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Embodiment 1: the synthesis of ethoxycyclohexanedione (3, see accompanying drawing)

[0020] Take 1.12 g of cyclohexanedione (2, 10.0 mmol) and dissolve it in 25 ml of absolute ethanol, add p-toluenesulfonic acid (1.0 mmol), stir and react at room temperature for 3 hours, and TLC detects that the reaction is complete. Add 30 ml of water, extract with dichloromethane (30mLx3), combine the organic phases, wash with saturated sodium bicarbonate solution, dry over anhydrous sodium sulfate, filter, concentrate, and purify by column chromatography to obtain a light yellow oily substance ethoxy-protected ring 1.23 grams of hexanedione, the yield is 88%.

Embodiment 2

[0021] Example 2: Synthesis of beta-hydroxycyclohexanone (5, see accompanying drawing) of bicyclic diterpene

[0022] Dissolve 140 mg (3, 1.0 mmol) of ethoxy-protected cyclohexanedione in 2 ml of anhydrous tetrahydrofuran, repeatedly fill and exhaust argon three times, exhaust the air, and cool down to -78 o c. LDA (3.0 mmol) was added and the reaction was kept stirring at this temperature for 30 minutes. Another 238 mg of (-) sclarealdehyde (4, see attached figure) was dissolved in 1 ml of anhydrous THF, slowly added dropwise to the above reaction system, and the stirring reaction was continued for 12 hours, and the reaction was detected by TLC. 5 ml of saturated ammonium chloride solution was added dropwise to the reaction system to quench the reaction, and stirring was continued at room temperature for 30 minutes. Extracted with ethyl acetate (10mLx3), combined organic phases, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and pu...

Embodiment 3

[0023] Embodiment 3: the synthesis of the basic skeleton (6, see accompanying drawing) of Puupehenone

[0024] Dissolve 189 mg (5,0.5 mmol) of beta-hydroxycyclohexanone of bicyclic diterpene in 4 ml of benzene, add trifluoroacetic acid (0.5 mmol) and stir for reaction at room temperature for 1 hour, and TLC detects that the reaction is complete. Add 10 ml of ethyl acetate, wash with saturated brine (10 mL x 3), dry the organic phase over anhydrous sodium sulfate, filter, concentrate, and purify by column chromatography to obtain 129 mg of white solid with a yield of 82%.

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Abstract

The invention relates to a synthesis method for a marine natural product Puupehenone, and belongs to the field of chemical synthesis. According to the synthesis method, (First) fragrant perillaldehyde and cyclohexanedione serve as initial raw materials; the synthesis method comprises the following steps: reacting the cyclohexanedione which is subjected to alkyl protection and the aldol of the (First) fragrant perillaldehyde to prepare beta-hydroxycyclohexanone of bicyclic sesquiterpanes; performing nucleophilic cyclization-elimination reaction of attacking a carbonyl by a hydroxyl under the catalysis of an acid to obtain a skeleton of the marine natural product Puupehenone; oxidizing the carbonyl at the ortho-position of an unsaturated ketene six-member ring carbonyl of the Puupehenone skeleton, and performing keto enol interconversion to obtain the final natural product Puupehenone. The synthesis method has the characteristics of few reaction steps, simple operation, high product selectivity, and application to industrial production and the like.

Description

technical field [0001] The invention relates to a synthetic method of Puupehenone, a marine natural product. Background technique [0002] The marine natural product Puupehenone was first isolated and extracted from deep-sea sponges Heteronema and Hyrtioseubnamma in 1979 (Pure and Applied Chemistry, 1979, 51(9): 1893-1900). Then in 1986, Shigeo Kohmoto and others separated and extracted it again from the deep-sea sponge Strongylophoraihartmani, and identified its structure through mass spectrometry, infrared and nuclear magnetic resonance techniques, and found that it is a cytotoxic sesquiterpene-sub Methylated quinone (TheJournalofOrganicChemistry, 1993,58(24):6565-6569), the structure is attached figure 1 . Its derivatives are important marine metabolites exhibiting various biological activities including cytotoxicity, antiviral, anticancer, antifungal, antimalarial, antituberculosis and immune regulation (Tetrahedron, 2000,56(7):949- 953; The Journal of Organic Chemist...

Claims

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Application Information

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IPC IPC(8): C07D311/78
CPCC07D311/78
Inventor 王洪双李惠静吴彦超周培林张振国
Owner 威海惠安康生物科技有限公司
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