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Synthesis method of marine natural product Puupehedione

A technology of natural products and synthetic methods, applied in the direction of organic chemistry, etc., can solve the problems of long reaction route, low yield, unsuitable for industrial production, etc., and achieve the effect of high total yield, good product selectivity, and few reaction steps

Active Publication Date: 2016-11-09
威海惠安康生物科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2005, Alvarez-Manzaneda et al achieved the synthesis of the correct configuration of the natural product through a palladium-catalyzed ring-closing synthesis strategy in 13 steps (Alvarez-Manzaneda E J, ChahbounR, Barranco Pérez I, et al. Organic letters, 2005 , 7(8): 1477-1480.), but the above-mentioned methods all have disadvantages such as long reaction routes, extremely low yields, and are not suitable for industrial production.

Method used

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  • Synthesis method of marine natural product Puupehedione

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Example 1: Synthesis of Perilla Hydrazone (2, see accompanying drawing)

[0018] Dissolve 2.38 g (1, 10.0 mmol) of (+) sclarealdehyde 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. After concentration, 3.98 g of white solid (+) clarylasulfonylhydrazone was obtained, with a yield of 98%.

Embodiment 2

[0019] Embodiment 2: the synthesis of skeleton compound (4, see accompanying drawing)

[0020] Take (+) 2.03 g (2, 5.0 mmol) of clarylar sulfonylhydrazone and dissolve it in 25 ml of anhydrous tetrahydrofuran, add 144 mg (0.125 mmol) of tetraphenylphosphine palladium and 2.07 g (15 mmol) of potassium carbonate and repeatedly charge Argon was purged three times to exhaust the air. Another 1.47 g (3.5 mmol) of iodo-1,2,4-trimethoxybenzene was dissolved in 5 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 50 ml of water to the reaction system, extract with ethyl acetate (30 mL x 3), combine the organic phases, wash with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and purify by column chromatography to obtain 1.47 g of white solid, The yield was 76%.

Embodiment 3

[0021] Embodiment 3: the synthesis of natural product Puupehedione (see accompanying drawing)

[0022] Take 1.16 g (4.3 mmol) of the skeleton compound and dissolve it in 10 ml of acetonitrile, cool to 0 o C. Take 3.29 g (6 mmol) of ammonium cerium nitrate and dissolve it in 20 ml of water, add the aqueous solution of ammonium cerium nitrate dropwise to the above system, stir and react for 0.5 hours, and TLC detects that the reaction is complete. Add 10 ml of water to the reaction system, extract with ethyl acetate (20 mL x 3), combine the organic phases, wash with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and purify by column chromatography to obtain 568 mg of a red solid, The yield was 58%. = 51 (c = 0.087 in MeOH); IR (film): ν max = 2922, 2359, 1653, 1646, 1603,1559, 1457, 1393, 1229, 1065, 668 cm−1; 1H NMR (400 MHz, CDCl3): δ = 6.31 (s,1H), 6.12 (s, 1H) , 5.95 (s, 1H), 1.54 (s, 3H), 1.24 (s, 3H), 0.96 (s, 3H),0.89 (s, 3H) ppm; 13C NMR (1...

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Abstract

The invention relates to a synthesis method of a marine natural product Puupehedione, and belongs to the field of chemical synthesis. (-)salvia sclarea aldehyde and 1-iodine-2,4,5-trialkoxy benzene are used as starting materials, (-)salvia sclarea aldehyde and p-toluenesulfonhydrazide generate salvia sclarea hydrazone 2, salvia sclarea hydrazone 2 and 1-iodine-2,4,5-trialkoxy benzene form a framework compound 4 of Puupehedione under the catalysis of palladium in a coupling manner, the framework compound 4 is oxidized into an intermediate quinine under the action of an oxidizing agent, and quinine and C-8 site hydroxyl are subjected to reaction, so as to realize cyclization, isomerization and dealcoholization reactions to obtain natural product Puupehedione in one step. The synthesis method has the characteristics of being few in reaction steps, simple and convenient to operate, good in product selectivity and suitable for industrial production.

Description

technical field [0001] The invention relates to a synthetic method of Puupehedione, a marine natural product. Background technique [0002] The marine natural product Puupehedione was first isolated and extracted from the deep-sea sponge Verongid sponge in 1993 (Hamann M T, Scheuer P J, et al. The Journal of organic chemistry, 1993, 58(24): 6565-6569.). It is a derivative of puupehenone, an active marine natural product, exhibiting various biological activities including cytotoxicity, antiviral, antifungal and immune regulation (LongleyRE, McConnelOJ, EssichE, HarmodyD. Journal of natural products, 1993, 56, 915. ; PopovAM, StekhovaSI, UtkinaNK, RebachukNM. Pharmaceutical chemistry journal. 1999, 33, 71.;PinaIC, SandersML, CrewsPJ. J. Nat. Barrero, A. F. et al. International journal of cancer, 2004, 110, 31.). [0003] There are few reports on the synthetic method of Puupehenone, and most of the synthetic methods have only obtained the epimer with the opposite orientation ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D311/78
CPCC07D311/78
Inventor 吴彦超王洪双李惠静刘颖
Owner 威海惠安康生物科技有限公司
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