Synthetic method for (S)-Virol A from water hemlock extract

A synthesis method and extract technology are applied in the field of asymmetric synthesis of hemlock extract-VirolA, which can solve the problems of difficulty in extraction and synthesis methods, decomposition and deterioration, and achieve cost reduction, simplification of reaction operations, efficient preparation process and environmental protection. Effect

Active Publication Date: 2016-02-24
HENAN AGRICULTURAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Since the extract of toxin is often a polyalkyne compound containing chiral alcoholic hydroxyl groups, it will decompose and deteriorate when exposed to air or exposed to light, and it is difficult to obtain by extraction and synthesis methods

Method used

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  • Synthetic method for (S)-Virol A from water hemlock extract
  • Synthetic method for (S)-Virol A from water hemlock extract
  • Synthetic method for (S)-Virol A from water hemlock extract

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Synthesis of (S)-VirolA(I):

[0027] Under nitrogen protection, in a 10mL Shrek tube equipped with a magnetic stirrer, add cuprous iodide (57mg, 0.3mmol), tetrakistriphenylphosphine palladium (86mg, 0.75mmol), 4,6-diyne- 1-Heptanol (III) (282mg, 1.5mmol) and 3mL of benzene, stirred well. After reacting at room temperature for 3 minutes, (S,1E,3E)-1-chloro-1,3-diene-5-decanol (II) (283.5mg, 1.5mmol) and triethylamine (2mL, 15mmol) were added sequentially , react overnight at room temperature. The reaction was quenched by adding 3 mL of saturated ammonium chloride solution. The aqueous phase was extracted with ether, the obtained organic phase was dried with anhydrous sodium sulfate, and the crude product was obtained by distillation under reduced pressure. Finally, it was purified by silica gel column chromatography (petroleum ether / ethyl acetate=10 / 1) to obtain 332 mg of a colorless liquid with a yield of 85%. [α] D 20 =+15.7(c1.1, MeOH). 1 HNMR (300MHz, CDCl 3 ...

Embodiment 2

[0029] Synthesis of (S)-4-hydroxyl-2-yne nonanoic acid methyl ester (VI):

[0030]In a 100ml Shrek bottle under nitrogen protection, 1.2777g (2mmol, 20% equiv) of Trost ligand and 1.1131g (4mmol, 40% equiv) of triphenylphosphine oxide were sequentially added. Cool to 0°C, add methyl propiolate 0.90ml (10mmol, 1.0equiv) successively, anhydrous toluene 15ml, slowly add dimethyl zinc solution 25ml (1.2mol / l, 30mmol, 3equiv), after the dropwise addition , continue to react for 30min. Lower the reaction system to -20°C, slowly add 4.8ml (40mmol, 4.0equiv) of hexanal dissolved in 15ml of toluene with a syringe pump within three hours, after the dropwise addition, continue to react for 5h, and detect by thin-layer chromatography. After the reaction was completed, 10ml of water was added, filtered with suction, extracted with ethyl acetate, washed with sodium chloride, dried over anhydrous sodium sulfate, precipitated, purified by column chromatography (ethyl acetate / petroleum ether=...

Embodiment 3

[0032] Synthesis of (S)-1-octyn-3-ol (VII):

[0033] In a 250ml three-necked flask, sequentially add (S)-4-hydroxy-2-alkyne methyl ester (VI) 0.9211g (5mmol, 1eq), tetrahydrofuran 25ml, and slowly add 1MaqLiOH (25mmol, 5eq) dropwise. Reaction 1h. Add 1MaqNaHSO to the system 4 50ml, after the dropwise addition, separate the liquids, extract with ethyl acetate, dry over anhydrous sodium sulfate, and remove the solvent. The obtained oil was dissolved in 12ml of acetonitrile, CuCl (6mmol, 1.2eq) was added, and reacted at room temperature for 13h. Add 120ml of diethyl ether, wash with brine, dry over anhydrous sodium sulfate, desolventize, and purify by column chromatography (ethyl acetate / petroleum ether=20 / 1) to obtain light oily liquid (S)-1-octyn-3-ol (VII) 0.536g, yield 85%. 1 HNMR (300MHz, CDCl 3 )δ4.30(m,1H),3.10(s,1H),2.40(d,J=2.1Hz,1H),1.75–1.54(m,2H),1.46–1.33(m,2H),1.33–1.11 (m,4H),0.83(t,J=7.0Hz,3H). 13 CNMR (75MHz, CDCl 3 )δ84.82,72.31,61.71,37.15,31.03,24.33,2...

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Abstract

The invention relates to a synthetic method for (S)-Virol A from a polyacetylene water hemlock extract. The synthetic method for (S)-Virol A from the polyacetylene water hemlock extract is an asymmetric synthetic method, and comprises the following steps: firstly, under catalysis of a chiral ligand, methyl propiolate and dimethyl zinc are reacted to prepare an alkynyl zinc reagent, hexanal is subjected to asymmetric addition reaction to obtain a chiral intermediate (S)-4- hydroxy-2-alkyne methyl nonanoate, through ester group removal to obtain acetylene, the processed intermediate is coupled with vinylidene chloride, then selective reduction is carried out to obtain a product, and finally the product is coupled with 4,6-diyne-1-heptanol to obtain the (S)-Virol A. The flow of the method is simple and easy to realize, and the method is environmental-friendly.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis of natural products, and in particular relates to an asymmetric synthesis method of hemlock extract (S)-VirolA. Background technique [0002] Plant secondary metabolites generally play a role in preventing the invasion of pests and other harmful organisms in plants. Hemlock (Apiaceae, Cress) contains a class of C17 polyacetylene compounds, which have strong cytotoxicity. In 1986, (S)-VirolA (Journal of Economic Entomology 1986, 79, 596) was found in the extract of hemlock, as shown in formula (I). Studies have shown that this type of compound is usually a potent, non-competitive γ-amino Butyric acid (GABA) receptor antagonists (Brainresearch 2001, 889, 174). [0003] [0004] Since the toxin extract is often a polyacetylenic compound containing a chiral alcoholic hydroxyl group, exposure to the air or exposure to light will cause its decomposition and deterioration, and it is diffic...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C33/048C07C29/34
CPCC07B53/00C07B2200/07C07C29/00C07C29/17C07C29/34C07C67/343C07C33/048C07C33/423C07C33/42C07C33/042C07C69/732
Inventor 那日松彭伟东刘佳郭线茹李洪连尹新明张猛李文明蒋士军郭艳艳刘炳杉王长青刘向阳卢世超侯伯男
Owner HENAN AGRICULTURAL UNIVERSITY
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