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Method for combining polysubstituted furan

A multi-substituted furan and compound technology, applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, organic chemistry, etc., can solve the problems of poor substrate compatibility and harsh conditions, and achieve the reaction Mild conditions and high yields

Inactive Publication Date: 2010-08-04
ZHEJIANG UNIV
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AI Technical Summary

Problems solved by technology

It has only recently been developed to use enynol as a raw material to construct a furan ring by isomeric cyclization under the action of metal catalysts such as strong base or gold, palladium, rhodium, etc., but generally only 2-alkyl substituted furans can be synthesized, and some reactions are not suitable for conditions. more demanding
In the literature (Marshall, J.A.; DuBay, W.J.J.Org.Chem.1993, 58, 3435.) although an example of a synthetic 2-alkenyl furan has been reported, the strongly basic reaction system is sensitive to many basic groups Unfavorable, with methoxymethyl ether as the leaving group, the compatibility of the substrate is poor

Method used

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  • Method for combining polysubstituted furan
  • Method for combining polysubstituted furan

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Add cuprous iodide (3.0mg, 0.015mmol, 6mol%), dichloroditriphenylphosphopalladium (7.0mg, 0.010mmol, 4mol%), 4-phenyl-3-n-pentyl to a dry reaction tube yl-4-iodo-3-butyn-2-ol (85.5mg, 0.25mmol), triethylamine (1mL), 2-methyl-3-butyn-2-ol (124.1mg, 1.5mmol, 6.0 equiv), dimethyl sulfoxide (1 mL), reacted at 40°C for 3 hours, quenched by adding 5 mL of saturated ammonium chloride solution, and extracted with diethyl ether (3 x 15 mL). The organic phase was washed once each with 5% hydrochloric acid, saturated sodium bicarbonate solution, and brine, dried over anhydrous sodium sulfate, filtered, spin-dried, and subjected to flash column chromatography (eluent petroleum ether / ethyl acetate=2 / 1), Collect the obtained crude product 7-methyl-4-phenyl-3-n-pentyl-5-yne-3-octene-2,7-diol in a bottle, and add 1 ml at a time to another bottle Dichloromethane, triphenylphosphine gold chloride (2.5mg, 0.005mmol, 2mol%), silver trifluoromethanesulfonate (1.6mg, 0.006mmol, 2mol%), stir...

Embodiment 2

[0023] According to the method described in Example 1, the difference is that the substrates and reagents used are: cuprous iodide (11.0mg, 0.058mmol, 2mol%), dichloroditriphenylphosphopalladium (3.7mg, 0.005mmol, 2mol%) %), 2-butyl-3-hexyl-4-iodo-2-propen-1-ol (80.0mg, 0.25mmol) / triethylamine (1mL), 2-methyl-3-butyne-2- Alcohol (43.3 mg, 0.52 mmol, 2 equiv) / dimethyl sulfoxide (1 mL), react at 40°C for 3 hours. The second step: two milliliters of dichloromethane, triphenylphosphine monochloride gold (7.2mg, 0.015mmol, 6mol%) / silver trifluoromethanesulfonate (4.0mg, 0.015mmol, 6mol%), stirred at room temperature for 3 hours , to obtain the product 46.5 mg, 72% yield, colorless liquid.

[0024] 1 H NMR (300MHz, CDCl 3 )δ7.08(s, 1H), 5.91(s, 1H), 2.36-2.28(m, 4H), 2.04(s, 3H), 1.88(s, 3H), 1.59-1.24(m, 12H), 0.98 -0.84(m, 6H); 13 C NMR (CDCl 3 , 75MHz) δ149.3, 136.6, 133.2, 126.0, 121.5, 112.2, 31.7, 31.6, 30.6, 29.2, 27.3, 23.5, 23.4, 22.7, 22.6, 20.0, 14.1, 13.9; IR (neat...

Embodiment 3

[0026]According to the method described in Example 1, the difference is that the substrates and reagents used are: cuprous iodide (1.0mg, 0.005mmol, 2mol%), dichloroditriphenylphosphopalladium (3.6mg, 0.005mmol, 2mol%) %), 2-n-pentyl-1-p-methylphenyl-3-iodo-2-propen-1-ol (85.2 mg, 0.25 mmol) / triethylamine (1 mL), 2-methyl-3- Butyn-2-ol (45.1 mg, 0.54 mmol, 2 equiv) / dimethyl sulfoxide (1 mL), react at 40°C for 10 hours. The second step: two milliliters of dichloromethane, triphenylphosphine gold chloride (2.4mg, 0.005mmol, 2mol%) / silver trifluoromethanesulfonate (1.4mg, 0.005mmol, 2mol%), stirred at room temperature for 1 hour , to obtain the product 61.1 mg, 87% yield, colorless liquid.

[0027] 1 H NMR (300MHz, CDCl 3 )δ7.50(d, J=7.8Hz, 2H), 7.19(d, J=8.1Hz, 2H), 6.13(s, 1H), 6.05(s, 1H), 2.62(t, J=7.8Hz, 2H), 2.35(s, 3H), 2.06(s, 3H), 1.91(s, 3H), 1.70-1.55(m, 2H), 1.44-1.27(m, 4H), 0.94-0.85(m, 3H) ; 13 C NMR (CDCl 3 , 75MHz) δ151.5, 146.5, 136.1, 134.6, 129.2, 125.1...

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Abstract

The invention relates to a method for combining polysubstituted furan; polysubstituted 3-iodine-2-propylene-1-alcohol and propargyl alcohol at tail end carry out Sonogashira coupling reaction to generate 4-alkyne-2-hexene-1, and 6-glycol carries out isomerism cyclization reaction to generate a series of polysubstituted furan compounds under the common catalysis of triphenylphosphine-gold chloride and silver trifloromethanesulfonic acid; the method has simple operation and is easy to obtain raw material and reagents, the reaction has high yield, multiple substituent groups can be introduced, the product is easy to separate and purify, therefore, the method is suitable for combining various polysubstituted furan compounds.

Description

technical field [0001] The present invention relates to a method for synthesizing multi-substituted furans, that is, through the Sogashira coupling reaction of 3-iodo-propen-1-ol and terminal propargyl alcohol to generate 4-alkyne-2-hexene-1,6-diol , and then under the co-catalysis of triphenylphosphine-gold chloride and silver trifluoromethanesulfonate, an isomerization cyclization reaction occurs to generate a series of multi-substituted furans. Background technique [0002] Furan is one of the most important intermediates in organic synthesis and one of the most common structural units in natural products. It has a variety of important physiological activities and has great development and utilization value in the field of biotechnology, medicine and pesticides. In the past, it was reported that the furan skeleton was constructed by using alkenone, acetylene ketone, cyclopropyl ketone, functionalized epoxy, etc. as substrates. It has only recently been developed to use e...

Claims

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Application Information

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IPC IPC(8): C07D307/36C07D307/42B01J31/24
Inventor 张小兵傅春玲麻生明
Owner ZHEJIANG UNIV
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