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Method for synthesizing 4-(1',3'-conjugated diene-2'-base)-2,5-dihydrofuran

A technology for conjugated diene and dihydrofuran, applied in the field of synthesizing 4--2, can solve the problems of low reaction yield and the like, and achieve the effects of easy separation and purification, high stereoselectivity and high yield

Inactive Publication Date: 2010-03-24
ZHEJIANG UNIV
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  • Application Information

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Problems solved by technology

The reaction yield of the 2,5-dihydrofuran synthesis method containing 1,3-conjugated diene structure reported in previous literature is relatively low (Ma, S.; Gao, W.J.Org.Chem.2002, 67, 6104; Hashmi, A.S.K.; Carmen Blanco, M.; Fischer, D.; Bats, J.W. Eur. J. Org. Chem. 2006, 1387.)

Method used

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  • Method for synthesizing 4-(1',3'-conjugated diene-2'-base)-2,5-dihydrofuran
  • Method for synthesizing 4-(1',3'-conjugated diene-2'-base)-2,5-dihydrofuran

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Embodiment 1

[0018] Palladium chloride (8.8mg, 0.05mmol), sodium iodide (75.1mg, 0.50mmol), 1-(1',2'-propadienyl)cyclohexanol (136.8mg, 0.99mmol) were added at room temperature, and N,N-dimethylacetamide (2mL), then set at 80°C for 5 hours to complete the reaction, cooled to room temperature, quenched with 10mL of water, extracted with ether (3x 25mL), saturated Na 2 S 2 o 3 aqueous solution, washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and flash column chromatography to obtain the product 3-(1'-cyclohexylidenemethylvinyl)-1-oxaspiro[4,5 ] Dec-3-ene 109.3 mg, yield 86%. The product is a colorless liquid.

[0019] 1 H NMR (400MHz, CDCl 3 )δ5.78(s, 1H), 5.74(s, 1H), 4.89(s, 1H), 4.86(s, 1H), 4.73(d, J=2.0Hz, 2H), 2.20(t, J=5.6Hz , 2H), 2.16(tJ=5.6Hz, 2H), 1.72-1.28(m, 16H).

Embodiment 2

[0021] According to the method described in Example 1, the difference is that the substrates and reagents used are: palladium chloride (9.0mg, 0.051mmol), sodium iodide (75.2mg, 0.50mmol), 1-methyl-3,4- Pentadiene-2-ol (100.1mg, 1.02mmol) and N,N-dimethylacetamide (2mL) gave the product 2,2-dimethyl-4-(1'-methylene-3' -Methyl-2'-butenyl)-2,5-dihydrofuran 60.2 mg, yield 66%. The product is a colorless liquid.

[0022] 1 H NMR (400MHz, CDCl 3 )δ5.81(s, 1H), 5.66(s, 1H), 4.95-4.90(m, 2H), 4.77-4.75(m, 2H), 1.81(s, 3H), 1.73(s, 3H), 1.31 (d, J=1.2Hz, 6H); 13 C NMR (100MHz, CDCl 3 )δ138.1, 138.0, 136.3, 131.8, 123.1, 114.6, 88.4, 73.4, 27.7, 26.0, 19.5; MS (m / z): 178 (M + , 4.08), 163 (M + -CH 3 , 78.58), 81(100); IR(neat, cm -1 ): 2970, 2928, 2858, 1660, 1634, 1594, 1450, 1287, 1038. HRMScalcd for C 12 h 19 O(M + +H): 179.1430; found: 179.1425.

Embodiment 3

[0024] According to the method described in Example 1, the difference is that the substrates and reagents used are: palladium chloride (8.8mg, 0.050mmol), sodium iodide (75.1mg, 0.50mmol), 1-ethyl-4,5- Hexadiene-3-ol (124.0mg, 0.98mmol) and N,N-dimethylacetamide (2mL) gave the product 2,2-diethyl-4-(1'-methylene-3' -Ethyl-2'-pentenyl)-2,5-dihydrofuran 98.0 mg, yield 85%. The product is a colorless liquid.

[0025] 1 H NMR (400MHz, CDCl 3 )δ5.77(s, 1H), 5.48(s, 1H), 4.91(s, 1H), 4.84(s, 1H), 4.76(d, J=2.0Hz, 2H), 2.18-2.07(m, 4H ), 1.66-1.49(m, 4H), 1.06(t, J=7.6Hz, 3H), 0.96(t, J=7.6Hz, 3H), 0.83(t, J=7.6Hz, 6H); 13 C NMR (100MHz, CDCl 3 )δ147.0, 140.1, 138.2, 128.7, 121.3, 113.6, 94.7, 75.1, 32.3, 28.5, 24.0, 13.4, 12.7, 8.4; MS (m / z): 234 (M + , 0.35), 205 (M + -C 2 h 5 , 100); IR(neat, cm -1 ): 2967, 2934, 1593, 1461, 1081, 1043. HRMS calcd for C 16 h 27 O(M + +H): 235.2056, found: 235.2050.

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Abstract

The invention relates to a method for high-stereoselectively synthesizing 4-(1', 3'-conjugated diene-2'-radical)-2, 5-dihydrofuran, namely synthesizing 4-(1', 3'-conjugated diene-2'-radical)-2, 5-dihydrofuran via the dimolecular coupling reaction of 2, 3-allenols under the catalysis of palladium chloride and sodium iodide. The method high-stereoselectively synthesizing 4-(1', 3'-conjugated diene-2'-radical)-2, 5-dihydrofuran has the advantages of simple operation, ready availability of raw material and reagent, high stereoselectivity of reaction, capability of inducing a plurality of substituent simultaneously, easy separation and purification of the product, which is suitable for synthesizing various substituted 4-(1', 3'-conjugated diene-2'-radical)-2, 5-dihydrofuran.

Description

technical field [0001] The present invention relates to a method for synthesizing 4-(1', 3'-conjugated dien-2'-yl)-2,5-dihydrofuran with high stereoselectivity, that is, through palladium chloride and iodide Under the catalysis of sodium, 2,3-alkenol undergoes bimolecular coupling reaction to synthesize 4-(1',3'-conjugated dien-2'-yl)-2,5-dihydrofuran. Background technique [0002] Both 2,5-dihydrofuran and 1,3-conjugated diene structures are important intermediates in organic synthesis and the most common structural units in natural products. They have various important physiological activities. In the field of biotechnology, It has great development and utilization value in medicine and pesticide. The reaction yield of the 2,5-dihydrofuran synthesis method containing 1,3-conjugated diene structure reported in previous literature is relatively low (Ma, S.; Gao, W.J.Org.Chem.2002, 67, 6104; Hashmi, A.S.K.; Carmen Blanco, M.; Fischer, D.; Bats, J.W. Eur. J. Org. Chem. 2006,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D307/28
Inventor 麻生明邓友前
Owner ZHEJIANG UNIV