Synthetic method of strigolactone (+/-)-GR24 and 4-substituted (+/-)-GR24

A technology of strigolactone and synthesis method, applied in the field of synthesis of strigolactone, can solve problems such as environmental pollution, large amount of catalyst, long reaction steps and the like

Active Publication Date: 2017-03-22
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The advantage of this method is that the raw materials are cheap and easy to get, but the disadvantage is that the total reaction steps are too long, the total yield is low, and more expensive heavy metal catalysts are used, and the amount of catalyst used in the ring-closing reaction is large
The disadvantage of this method is that the raw materials are relatively expensive, and the use of toxic organ

Method used

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  • Synthetic method of strigolactone (+/-)-GR24 and 4-substituted (+/-)-GR24
  • Synthetic method of strigolactone (+/-)-GR24 and 4-substituted (+/-)-GR24
  • Synthetic method of strigolactone (+/-)-GR24 and 4-substituted (+/-)-GR24

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Taking the synthesis of (±)-GR24 as an example, the synthesis method is as follows:

[0037] 1. Dissolve 1.030g (8.434mmol) of benzoic acid, 189mg (0.842mmol) of palladium acetate and 4.412g (19.332mmol) of dipotassium hydrogen phosphate in 28mL (0.400mol) of dibromomethane, and stir and react at 130°C for 36 hours. Stirring was stopped, cooled to room temperature, filtered, concentrated under reduced pressure, purified by column chromatography (V PE :V EA =2:1), a white solid—984 mg of the intermediate of formula I was obtained, with a yield of 87%.

[0038]

[0039] The obtained product is analyzed by hydrogen spectrum and carbon spectrum with AVANCF 400MHz nuclear magnetic resonance instrument of German Bruker company, and the characterization results are: 1 H NMR (300MHz, CDCl 3 )δ (ppm): 7.94 (d, J = 7.5Hz, 1H), 7.69 (t, J = 7.5Hz, 1H), 7.49-7.57 (m, 2H), 5.33 (s, 2H); 13 C NMR (100MHz, CDCl 3 )δ (ppm): 171.04, 146.48, 133.96, 128.97, 125.68, 122.06, 69.60....

Embodiment 2

[0057] Taking the synthesis of (±)-4-OH-GR24 as an example, the synthesis method is as follows:

[0058] Steps 1 to 4 of this embodiment are the same as those of Embodiment 1. In step 5, under an argon atmosphere, 85.6 mg (0.450 mmol) of the intermediate of formula IV was dissolved in 5 mL of dichloromethane, 45.3 mg (0.090 mmol) of iron triflate was added, and the reaction was stirred at room temperature 12 hour, stop stirring, add 20mL dichloromethane for dilution, wash twice with saturated aqueous sodium bicarbonate solution, and wash once with saturated aqueous sodium chloride solution, dry through anhydrous magnesium sulfate, filter, concentrate, and purify by column chromatography (V PE :V EA=1:2) to obtain 54.8 mg of a colorless viscous intermediate of formula V-2 with a yield of 64%.

[0059]

[0060] The obtained product is analyzed by hydrogen spectrum and carbon spectrum with AVANCF 600MHz nuclear magnetic resonance instrument of German Bruker company, and the ...

Embodiment 3

[0067] Taking the synthesis of (±)-4-SPh-GR24 as an example, the synthesis method is as follows:

[0068] Steps 1-4 of this embodiment are the same as those of Embodiment 1. In step 5, under an argon atmosphere, 83 mg (0.436 mmol) of the intermediate of formula IV was dissolved in 9 mL of dichloromethane, 110 mg (0.218 mmol) of iron triflate, 132 μL (1.308 mmol) of thiophenol were added Stir the reaction at room temperature for 24 hours, stop the reaction, add 20 mL of dichloromethane to dilute, wash twice with saturated aqueous sodium bicarbonate solution, once with saturated aqueous sodium chloride solution, dry over anhydrous magnesium sulfate, filter, concentrate, and column chromatography Purification (V PE :V EA =3:1), to obtain light yellow liquid - 86.2 mg of intermediate of formula V-3, the yield was 70%.

[0069]

[0070] The obtained product is analyzed by hydrogen spectrum and carbon spectrum with AVANCF 400MHz nuclear magnetic resonance instrument of German ...

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Abstract

The invention discloses a synthetic method of strigolactone (+/-)-GR24 and 4-substituted (+/-)-GR24. The method comprises the following steps: benzoic acid which is used as a raw material reacts with dibromomethane to obtain an intermediate as shown in the formula I; the intermediate I undergoes diisobutylaluminium hydride reduction to obtain an intermediate as shown in the formula II; the intermediate II and (2-carboxyethyl)triphenylphosphonium bromide undergo coupling under the action of alkali so as to obtain an intermediate as shown in the formula III; the intermediate III reacts with Dess-Martin periodinane to obtain an intermediate as shown in the formula IV; the intermediate IV undergoes cyclization under the action of an acid catalyst or reacts with a nucleophilic reagent so as to obtain ABC tricyclic lactone, namely an intermediate as shown in the formula V; the intermediate V and ethyl formate undergo a formylation reaction to obtain an intermediate VI; and the intermediate VI and bromobutenolide undergo coupling so as to obtain (+/-)-GR24 and 4-substituted (+/-)-GR24. The raw materials used in the synthetic method are cheap and easily available; the operation is simple; reaction conditions are mild; safety is high; the catalyst used in the invention is environment-friendly; tricyclic lactone can be constructed by one-step tandem cyclizaiton reaction; the reaction route is short; and overall yield is high. Thus, total cost is greatly reduced. The synthetic method meets requirements of mass synthesis.

Description

technical field [0001] The invention belongs to the technical field of strigolactone synthesis, in particular to a synthesis method of strigolactone (±)-GR24 and 4-substituted (±)-GR24. Background technique [0002] Strigolactones are a class of sesquiterpenoids discovered in the study of plant root exudates. It is a general term for some natural strigyl alcohol compounds and synthetic analogues. (±)-GR24(3-(4-Methyl-5-oxo-2,5-dihydrofuran-2-oxymethyl)-3,3a,4,8b-tetrahydro-indeno(1,2 -b) Furan-2-one, referred to as GR24) is the first artificially synthesized strigolactone, which is composed of hexapentapentatricyclic lactone coupled with bromobutenoic acid lactone through an enol ether bond. linked together. Studies have shown that (±)-GR24 and 4-substituted (±)-GR24 have a variety of biological activities, and have good application prospects in promoting plant germination, regulating plant branching, and inhibiting breast cancer cell proliferation. The structures of (±)...

Claims

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Application Information

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IPC IPC(8): C07D307/93
CPCC07D307/93
Inventor 张琦陈月月马敏艳康秀琴柴永海
Owner SHAANXI NORMAL UNIV
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