CN101812046B - A kind of furan compound, synthesis method and application - Google Patents

Abstract

The invention relates to a chiral furan compound, which is a chiral furan compound synthesized with high efficiency and high enantioselectivity through intramolecular oxa-Michael reaction of cyclohexadienone derivatives catalyzed by chiral phosphoric acid. The furan compound can be For the preparation of long-tubular pseudojasmonin natural products. The method has mild reaction conditions and is easy to operate. In addition, there is no need to add any metal salt compounds in the reaction, which facilitates the production and processing of potential biologically active compounds. And the yield of the reaction is also good (generally 71%-93%), and the enantioselectivity is high (generally 61%->99%).

Description

A kind of furan compound, synthesis method and application

technical field

The invention relates to a chiral furan compound, which is a chiral furan compound synthesized with high efficiency and high enantioselectivity through intramolecular oxa-Michael reaction of cyclohexadienone derivatives catalyzed by chiral phosphoric acid. The furan compound can be For the preparation of long-tubular pseudojasmonin natural products. the

Background technique

S.，Chem.Rev.2008，37，1218.]。因而发展一种操作方便，特别是高效率、高对映选择性的不对称氧杂Michael反应是这方面的重点和难点。我们发展 利用手性磷酸这一有机小分子催化剂，在数分钟到数小时内催化分子内氧杂Michael反应，对合成手性氧杂环状化合物如1，4-氧杂化合物及呋喃化合物有着重要的意义。另外，氧杂Michael产物如呋喃化合物通过进一步转化，可以简单高效地合成长管假茉莉素类化合物，该类化合物可以从植物长管假茉莉中提取获得，该植物在中国常常用来治疗疟疾和风湿病[(a)Tian，J.；Zhao，Q.-S.；Zhang，H.-J.；Lin，Z.-W.；Sun，H.-D.J.Nat.Prod.1997，60，766.(b)Cheng，H.-H.；Wang，H.-K.；Ito，J.；Bastow，K.F.T.Y.；Nakanishi，Y.；Xu，Z.；Luo，T.-Y.；Lee，K.-H.J.Nat.Prod.2001，64，915.]。但是关于长管假茉莉素类化合物的不对称合成只有少量的报道，且步骤繁锁[(a)Honzumi，M.；Kamikubo，T.；Ogasawara，K.Synlett1998，1001.(b)Canto，M.；deMarch，P.；Figueredo，M.；Font，J.；Rodriguez，S.；Alarez-Larena，A.；Piniella，J.F.Tetrahedron：Asymmetry2002，13，455.(c)You，Z.；Hoveyda，A.H.；Snapper，M.L.Angew.Chem.Int.Ed.2009，48，547.(d)Wenderski，T.A.；Huang，S.-L.；Pettus，T.R.R.J.Org.Chem.2009，74，4104.]。我们将该方法学运用到这些天然产物的合成中，简单高效地合成了具有光学活性的长管假茉莉素类类化合物。  In recent years, organic small molecule catalysis has attracted widespread attention from academia and industry all over the world due to its advantages of easy synthesis, convenient structure modification, and no heavy metal residue [(a) Seayad, J.; List, B.Org .Biomol.Chem.2005,3,719-724.(b) Dalko, PI; Moisan, L.Angew.Chem.Int.Ed.2004,43,5138-5175.], wherein by chiral phosphoric acid as catalyst The achieved asymmetric catalysis has achieved rapid development in recent years [(a) Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K.Angew.Chem.Int.Ed.2004, 43 , 1566-1568.(b) Uraguchi, D.; Terada, MJAm.Chem.Soc. 2004, 126, 5356-5357.(c) Uraguchi, D.; 2004, 126, 11804-11805.]. In this field, we developed the intramolecular oxa-Michael reaction of cyclohexadienone derivatives catalyzed by chiral phosphoric acid, which can synthesize chiral cyclic oxa compounds with high efficiency and high enantioselectivity. , such as 1,4-oxa compounds and furan compounds. Oxygen heterocyclic compounds are present in a large number of biologically active natural products and drug molecules [(a) Tang, Y.; Oppenheimer, J.; Song, Z.-L.; You, L.-F.; Zhang , X.-J.; Hsung, RPTetrahedron2006, 62, 10785. (b) Shi, Y.-L.Shi, M.Org.Biomol.Chem.2007, 5, 1499.], but due to the oxa-Michael reaction often There is a certain reversibility that hinders its asymmetric methodological development [Nising, CF;

S., Chem. Rev. 2008, 37, 1218.]. Therefore, the development of a convenient, especially high-efficiency, high-enantioselective asymmetric oxa-Michael reaction is the focus and difficulty in this regard. We have developed and utilized chiral phosphoric acid, a small organic molecule catalyst, to catalyze intramolecular oxa-Michael reactions within minutes to hours, which is important for the synthesis of chiral oxygen heterocyclic compounds such as 1,4-oxa compounds and furan compounds. meaning. In addition, through further transformation of oxa-Michael products such as furan compounds, long-tubular pseudojasmonins can be synthesized simply and efficiently. Rheumatism [(a) Tian, J.; Zhao, Q.-S.; Zhang, H.-J.; Lin, Z.-W.; Sun, H.-DJ Nat.Prod.1997, 60, 766. (b) Cheng, H.-H.; Wang, H.-K.; Ito, J.; Bastow, KFTY; Nakanishi, Y.; Xu, Z.; Luo, T.-Y.; Lee, K. -HJ Nat.Prod.2001, 64, 915.]. But there are only a small number of reports about the asymmetric synthesis of long-tube pseudojasmonoids, and the steps are cumbersome [(a) Honzumi, M.; Kamikubo, T.; Ogasawara, K.Synlett1998, 1001.(b) Canto, M .; deMarch, P.; Figueredo, M.; Font, J.; Rodriguez, S.; Alarez-Larena, A.; ; Snapper, ML Angew. Chem. Int. Ed. 2009, 48, 547. (d) Wenderski, TA; Huang, S.-L.; Pettus, TRRJ Org. Chem. 2009, 74, 4104.]. We applied this methodology to the synthesis of these natural products and synthesized optically active long-tubular pseudojasmonoids in a simple and efficient manner.

Contents of the invention

The object of the present invention is to provide a compound containing furan;

The object of the present invention or provide a kind of method for effectively synthesizing above-mentioned furan compound;

Another object of the present invention is to provide a method for asymmetrically synthesizing elongated pseudojasmonins. the

A kind of furan compound of the method of the present invention has following structural formula:

Wherein R ¹ is arbitrarily selected from H, C1-C16 alkyl; wherein R ² is arbitrarily selected from OH, OOH, C ₃ -C ₁₆ cycloalkyl, C ₄ -C ₁₀ containing N, O or S heterocycle Base, aryl, R substituted aryl; said aryl is phenyl or naphthyl; R is C ₁ -C ₄ alkyl, C ₁ -C ₄ perfluoroalkyl, halogen or C ₁ - C ₄ alkoxy; wherein X is arbitrarily selected from CH ₂ or OCH ₂ .

A kind of furan-containing compound of the present invention is to take cyclohexadienone derivative as raw material, under the presence of organic solvent, take chiral phosphoric acid as catalyst reaction to prepare, can be represented by following reaction formula:

其中R⁸，R⁹，R¹⁰，  The further description of this reaction is that in an organic solvent and at a temperature of -78°C to 100°C, a cyclohexadienone derivative is used as a raw material, and a chiral phosphoric acid is used as a catalyst to react for 5 minutes to 48 hours. The molar ratio of enone derivatives and chiral phosphoric acid is 1:0.01-0.5, and the molar ratio of the recommended reaction is: cyclohexadienone derivatives: chiral phosphoric acid=1:0.05-0.2. The recommended reaction temperature is: -60 °C to 25 °C. The general structural formula of the catalyst is (for any optically pure structure, not limited by the illustration):

where R ⁸ , R ⁹ , R ¹⁰ ,

R ¹¹ and R ¹² are randomly selected from H, C1-C16 alkyl, triphenylsilyl, aryl, R-substituted aryl; the aryl is phenyl, naphthyl, anthracenyl or phenanthrenyl; R is C ₁ -C ₄ alkyl, C ₁ -C ₄ perfluoroalkyl, halogen or C ₁ -C ₄ alkoxy.

In the method of the present invention, the water is distilled water. Described organic solvent can be polar or non-polar solvent, as benzene, carbon tetrachloride, sherwood oil, tetrahydrofuran, dimethylformamide, ether, methylene dichloride, chloroform, toluene, xylene, cyclohexane alkanes, n-hexane, n-heptane, dioxane or acetonitrile, etc. the

The product obtained by adopting the method of the present invention can be separated and purified through methods such as recrystallization, thin layer chromatography, column chromatography and vacuum distillation. If the method of recrystallization is used, the recommended solvent is a mixed solvent of polar solvent and non-polar solvent. The recommended solvent can be dichloromethane-n-hexane, isopropanol-petroleum ether, ethyl acetate-petroleum ether, ethyl acetate-n-hexane, isopropanol-ethyl acetate-petroleum ether, etc. solvent. With thin-layer chromatography and column chromatography, the developer used is a mixed solvent of polar solvent and non-polar solvent. Recommended solvents can be mixed solvents such as isopropanol—petroleum ether, ethyl acetate—petroleum ether, ethyl acetate—n-hexane, isopropanol—ethyl acetate—petroleum ether, and their volume ratios can be respectively : Polar solvent: non-polar solvent = 1: 0.1-500. For example: ethyl acetate: petroleum ether = 1: 0.1-50, isopropanol: petroleum ether = 1: 0.1-500. the

The furan compound of the present invention can be used for preparing long-tube pseudojasmonoid compounds, and its structural formula is as follows:

Long-tube pseudojasmone F, long-tube pseudojasmone C or long-tube pseudojasmone D. the

Further specifically describe the method of the present invention as follows: in an organic solvent and at room temperature, the aforementioned furan compound of the present invention reacts with a reducing agent for 1-72 hours to obtain the long tube pseudojasmonin F compound, and the furan compound and The molar ratio of the reducing agent is 1:1-5; the reducing agent is sodium sulfite, sodium thiosulfate, triphenyl phosphite or triphenylphosphine. the

In an organic solvent and at room temperature, the above-mentioned elongated pseudojasmonin F compound was hydrogenated on palladium carbon for 1-72 hours to obtain the elongated pseudojasmonin C compound, and the elongated pseudojasmonin F compound and palladium carbon 1: 0.01-0.2. the

In an organic solvent and at room temperature, the furan compound as described above is reacted with potassium carbonate, sodium carbonate or benzyltrimethylammonium hydroxide for 1-72 hours, followed by a reducing agent for 1-72 hours to obtain the long pipe false jasmine element D compound; the reducing agent is triethylaluminum borohydride, aluminum amalgam or lithium aluminum tetrahydride; the mol ratio of the furan compound to potassium carbonate, sodium carbonate or benzyltrimethylammonium hydroxide is 1:0.1-0.5; the molar ratio of the furan compound to the reducing agent is 1:1-10. the

The present invention provides an effective chiral oxygen heterocyclic compound, such as 1,4-oxa A compound and a method for a furan compound; wherein the furan product can be efficiently prepared for long-tube pseudojasmonin compounds through simple transformation. The synthesis method has the advantages of relatively easy to obtain catalyst, high catalytic activity, wide application range of substrates, high enantioselectivity of products, mild reaction conditions and simple operation. In addition, there is no need to add any metal salt compounds in the reaction, which is beneficial to the production and treatment of medicines. And the yield of the reaction is also good (generally 71%-93%), and the enantioselectivity is high (generally 61%-99%). the

Detailed ways

The following examples will help to understand the present invention, but do not limit the content of the present invention. the

Embodiment 1: Preparation of chiral phosphoric acid

Under the protection of argon at room temperature, dissolve the derivative of BINOL (0.5mmol) in 1mL of dry pyridine in a dry reaction tube, and slowly drop (1.0mmol) of phosphorus oxychloride under the condition of rapid stirring Added to the system, stirred at room temperature for 3 hours. 1 mL of water was slowly added dropwise to the system, and stirred at room temperature for 30 minutes. Dichloromethane was added to dissolve, washed with 1N aqueous hydrochloric acid (3×10 mL), the organic layer was dried over anhydrous sodium sulfate, the solvent was spun off under reduced pressure, and the residue was separated by column chromatography to obtain the product. the

(S)-3,3′-[3,5-bis(trifluoromethyl)phenyl]2-1,1′-binaphthol phosphate

(S)-3,3′-[3,5-Bis(trifluoromethyl)phenyl]2-1,1′-binaphthyl phosphate

Solid, 89% yield (yield). IR (CHCl ₃ ) 1620, 1501, 1474, 1379, 1325, 1281, 1246, 1178, 1140, 1109, 1084, 1024, 988, 964, 891, 870 ^{, 867cm -1} . ¹ H NMR (400MHz, CDCl3) δ = 8.01 (s, 8H), 7.61-7.58 (m, 4H), 7.42-7.39 (m, 4H). ³¹ P NMR (189MHz, CDCl ³ ) δ = ^4.61.13 C NMR (100 MHz, CDCl ₃ ) δ=143.5 (d, J _PC =9.3 Hz), 138.6, 132.3, 132.0, 131.4, 131.4 (q, J _CF =33.4 Hz), 131.1 (d, J _PC =3.1 Hz) , 129.9, 128.7, 127.6, 127.1, 126.8, 123.1 (q, J _CF = 272.9 Hz), 122.5 (d, J _PC = 1.9 Hz), 121.5. ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ = 96.3.

Example 2: Intramolecular Oxa-Michael Reaction Catalyzed by Chiral Phosphoric Acid

分子筛(150mg)和二氯甲烷(6mL)。 室温下反应至原料消失(TLC检测)。反应液经硅藻土过滤，固体用二氯甲烷洗涤，滤液减压旋去溶剂，残留物经板层析分离得产物。  Under argon protection, add cyclohexadienone derivative (0.3mmol), chiral phosphoric acid catalyst (22.8mg, 10mol%), activated

Molecular sieves (150 mg) and dichloromethane (6 mL). React at room temperature until the starting material disappears (TLC detection). The reaction solution was filtered through diatomaceous earth, the solid was washed with dichloromethane, the filtrate was spun to remove the solvent under reduced pressure, and the residue was separated by plate chromatography to obtain the product.

P1: (4aS, 8aR)-8a-methyl-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

P1: (4aS, 8aR)-8a-methyl-2, 3, 4a, 5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

White solid, 91% yield, 94% ee [62% yield, 99% ee (ethyl acetate/petroleum ether, recrystallized)].Analytical data for P1 (99% ee): [α] _D ²⁰ =+23.6° (c=0.5, CHCl ₃ ). Mp=105-106°C. ¹ H NMR (300MHz, CDCl ₃ ) δ1.39(s, 3H), 2.59 (dd, J=3.0, 17.4Hz, 1H), 2.69( dd, J=3.0, 17.1Hz, 1H), 3.63-3.73(m, 3H), 3.80-3.83(m, 1H), 3.89-3.91(m, 1H), 6.11(d, J=10.5Hz, 1H) , 6.70 (dd, J=3.0, 10.5Hz, 1H); ¹³ C NMR (75MHz, CDCl ₃ ) δ24.5, 42.0, 62.9, 66.2, 71.9, 78.2, 130.5, 152.3, 195.7; IR (KBr) 2977, 2914, 2863, 1674, 1414, 1386, 1350, 1287, 1233, 1124, 1097, 1023, 953, 946, 791, 697cm ^-1 ; HRMS (EI): calculated value of high-resolution mass spectrum C ₉ H ₁₂ O ₃ : 168.0786 .Measured value: 168.0786. Chiral test conditions: Daicel Chiralpak OB-H (25cm), n-hexane/isopropanol=90/10, 0.6mL/min ^-1 , λ=220nm, t _R (major)=22.04min , t _R (minor) = 26.49 min.

P2: (4aS, 8aR)-8a-ethyl-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

P2: (4aS, 8aR)-8a-ethyl-2, 3, 4a, 5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

Semi-solid, 91% yield, 78% ee. Analytical data for P2: [α] _D ²⁰ =+27.7° (c=1.0, CHCl ₃ ). ¹ H NMR (400MHz, CDCl ₃ ) δ1.04(t, J =7.2Hz, 3H), 1.71-1.75(m, 2H); 2.55-2.71(m, 2H), 3.67-3.70(m, 3H), 3.79-3.86(m, 1H), 3.93-3.95(m, 1H ), 6.13 (dd, J=1.2, 10.4Hz, 1H), 6.73 (dd, J=2.8, 10.4Hz, 1H); ¹³ C NMR (100MHz, CDCl ₃ ) δ7.2, 31.4, 41.8, 62.8, 66.2 , 73.8, 76.9, 130.9, 152.3, 195.8; IR (KBr) 2973, 2920, 2866, 1686, 1411, 1382, 1275, 1126, 1096, 992, 966, 926, 793, 697cm ^-1 ; HRMS (EI): Calculated value of high-resolution mass spectrum C ₁₀ H ₁₄ O ₃ : 182.0943. Measured value: 182.0941 Chiral test conditions: DaicelChiralpak OB-H (25cm), n-hexane/isopropanol=90/10, 0.6mL/min ^-1 , λ = 220 nm, t _R (major) = 22.21 min, t _R (minor) = 26.78 min.

P3: (4aS,8aR)-8a-isopropyl-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

P3: (4aS, 8aR)-8a-isopropyl-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

Pale yellow solid, 71% yield, 61% ee. Analytical data for P3: [α] _D ²⁰ = +1.6° (c = 0.6, CHCl ₃ ). Mp = 65-67°C. ¹ H NMR (300 MHz, CDCl ₃ )δ1.03(d, J=6.9Hz, 3H), 1.08(d, J=6.9Hz, 3H), 1.95(heptet, J=6.9Hz, 1H), 2.52-2.73(m, 2H), 3.64- 3.71(m, 3H), 3.80-3.88(m, 1H), 4.13-4.16(m, 1H), 6.14(d, J=10.5Hz, 1H), 6.82(d, J=10.5Hz, 1H); ¹³ C NMR (75MHz, CDCl ₃ ) δ16.8, 17.2, 35.6, 41.3, 62.6, 66.2, 75.0, 75.5, 130.6, 153.8, 195.8; IR (KBr) 2957, 2918, 2860, 1683, 1379, 1279, 1261, 1222, 1137, 1101, 998, 922, 802, 774, 690cm ^-1 ; HRMS (EI): calculated value of high resolution mass spectrum C ₁₁ H ₁₆ O ₃ : 196.1099. Measured value: 196.1097. Chiral test conditions: Daicel Chiralpak OB -H (25cm), n-hexane/isopropanol=90/10, 0.6mL/min ^-1 , λ=220nm, t _R (major)=18.93min, t _R (minor)=21.81min.

P4: (4aS, 8aS)-8a-phenyl-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

P4: (4aS, 8aS)-8a-phenyl-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

White solid, 92% yield, 91% ee [68% yield, 99% ee (ethyl acetate/petroleum ether, recrystallized)].Analytical data for P4 (99% ee): [α] _D ²⁰ =+171.6° (c=0.39, CHCl ₃ ). Mp=123-124°C. ¹ H NMR (300MHz, CDCl ₃ ) δ2.45 (d, J=3.0Hz, 2H), 3.84-3.91 (m, 3H), 4.03- 4.07(m, 2H), 6.48(d, J=10.5Hz, 1H), 6.78(dd, J=3.0, 10.5Hz, 1H), 7.35-7.43(m, 3H), 7.54-7.57(m, 2H) ; ¹³ C NMR (75MHz, CDCl ₃ ) δ41.2, 62.8, 66.3, 76.9, 79.3, 126.7, 128.6, 128.7, 132.9, 138.4, 148.7, 196.4; IR (KBr) 2968, 2916, 2868, 1685, 1490, 1446, 1401, 1263, 1218, 1120, 1087, 979, 917, 777, 758, 696cm ^-1 ; HRMS (EI): calculated value of high resolution mass spectrum C ₁₄ H ₁₄ O ₃ : 230.0943. Measured value: 230.0942. Chirality Test conditions: Daicel Chiralpak AS-H (25cm), n-hexane/isopropanol=80/20, 1.0mL/min ^-1 , λ=220nm, t _R (major)=22.44min, t _R (minor)=34.19min .

P5: (4aS, 8aS)-8a-(4-fluorophenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

P5: (4aS, 8aS)-8a-(4-fluorophenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

White solid, 91% yield, 90% ee. Analytical data for P5: [α] _D ²⁰ = +137.1° (c = 0.5, CHCl ₃ ). Mp = 159-160°C. ¹ H NMR (300MHz, CDCl ₃ ) δ2.53-2.37(m, 2H), 3.84-3.89(m, 3H), 3.99-4.10(m, 2H), 6.48(d, J=10.5Hz, 1H), 6.76(dd, J=3.0, 10.5 Hz, 1H), 7.05-7.11 (m, 2H), 7.51-7.56 (m, 2H); ¹³ C NMR (75MHz, CDCl ₃ ) δ41.1, 62.9, 66.3, 76.5, 79.3, 115.5 (d, J= 21.3Hz), 128.6(d, J=8.2Hz), 133.1, 134.3(d, J=3.3Hz), 148.3, 162.7(d, J=246.6Hz), 196.15; ¹⁹ F NMR (282MHz, CDCl ₃ )δ -113.42; IR (KBr) 3072, 2970, 2914, 2865, 1685, 1604, 1509, 1491, 1225, 1161, 1120, 1102, 1037, 980, 920, 841, 771, 689cm ^-1 ; HRMS (EI): Calculated value of high-resolution mass spectrum C ₁₄ H ₁₃ O ₃ F: 248.0849. Measured value: 248.0846. Chiral test conditions: Daicel Chiralpak AS-H (25cm), n-hexane/isopropanol=80/20, 1.0mL/min ^{- 1} , λ=220 nm, t _R (major)=72.04 min, t _R (minor)=102.38 min.

P6: (4aS, 8aS)-8a-(4-chlorophenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

P6: (4aS, 8aS)-8a-(4-chlorophenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

White solid, 90% yield, 91% ee. Analytical data for P6: [α] _D ²⁰ = +162.7° (c = 0.4, CHCl ₃ ). Mp = 135-136°C. ¹ H NMR (300MHz, CDCl ₃ ) δ2.37-2.47(m, 2H), 3.84-3.89(m, 3H), 3.96-4.07(m, 2H), 6.48(d, J=10.5Hz, 1H), 6.75(dd, J=2.7, 10.5 Hz, 1H), 7.37 (d, J=8.7Hz, 2H), 7.49 (d, J=8.7Hz, 2H); ¹³ C NMR (75MHz, CDCl ₃ ) δ41.1, 62.8, 66.3, 76.6, 79.2, 128.2, 128.8, 133.2, 134.8, 137.1, 148.1, 196.1; IR (KBr) 2966, 2916, 2863, 1692, 1486, 1402, 1283, 1262, 1123, 1094, 1014, 977, 923, 826, 728; HRMS ( EI): Calculated value of high-resolution mass spectrum C ₁₄ H ₁₃ O ₃ Cl: 264.0553. Measured value: 264.0558. Chiral test conditions: Daicel Chiralpak AS-H (25cm), n-hexane/isopropanol=80/20, 1.0mL /min ⁻¹ , λ=220 nm, t _R (major)=81.40 min, t _R (minor)=105.82 min.

P7: (4aS, 8aS)-8a-(4-bromophenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

P7: (4aS, 8aS)-8a-(4-bromophenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

White solid, 84% yield, 90% ee [64% yield, 99% ee (ethyl acetate/petroleum ether, recrystallized). Analytical data for P7 (99% ee): [α] _D ²⁰ =+187.0°( c=0.5, CHCl ₃ ). Mp=146-147°C. ¹ H NMR (300 MHz, CDCl ₃ ) δ2.37-2.53 (m, 2H), 3, 84-3.87 (m, 3H), 4.09-4.93 ( m, 2H), 6.49(d, J=10.5Hz, 1H), 6.74(dd, J=3.0, 10.5Hz, 1H), 7.42(d, J=8.4Hz, 2H), 7.52(d, J=8.4 Hz, 2H); ¹³ C NMR (75MHz, CDCl ₃ ) δ41.1, 62.8, 66.3, 76.5, 79.1, 122.9, 128.5, 131.7, 133.2, 137.6, 148.0, 196.0; IR (KBr) 2916, 2864, 1695, 1481, 1398, 1284, 1263, 1124, 1115, 1033, 1002, 977, 824, 677cm ^-1 ; HRMS (EI): calculated value of high resolution mass spectrum C ₁₄ H ₁₃ O ₃ Br: 308.0048. Measured value: 308.0045. Hand Performance test conditions: Daicel Chiralpak AS-H (25cm), n-hexane/isopropanol=80/20, 1.0mL/min ^-1 , λ=220nm, t _R (major)=71.23min, t _R (minor)= 98.27min.

P8: (4aS,8aS)-8a-(4-methylphenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

P8: (4aS, 8aS)-8a-p-tolyl-2, 3, 4a, 5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

White solid, 91% yield, 92% ee [72% yield, 99% ee (ethyl acetate/petroleum ether, recrystallized)].Analytical data for P8 (99% ee): [α] _D ²⁰ =+212.6° (c=1.1, CHCl ₃ ). Mp=164-165° C. ¹ H NMR (300 MHz, CDCl ₃ ) δ 2.36 (s, 3H), 2.45 (d, J=3.0 Hz, 2H), 3.83-3.90 ( m, 3H), 4.00-4.05(m, 2H), 6.47(d, J=10.5Hz, 1H), 6.77(dd, J=2.7, 10.5Hz, 1H), 7.20(d, J=8.4Hz, 2H ), 7.42 (d, J=8.4Hz, 2H); ¹³ C NMR (75MHz, CDCl ₃ ) δ21.0, 41.3, 62.8, 66.4, 76.8, 79.4, 126.6, 129.3, 132.8, 135.5, 138.6, 148.9, 196.6 ; IR (KBr) 2974, 2916, 2864, 1681, 1517, 1447, 1404, 1263, 1106, 1083, 978, 921, 821, 687cm ^-1 ; HRMS (EI): calculated value of high resolution mass spectrum C ₁₅ H ₁₆ O ₃ : 244.1099. Measured value: 244.1102; Chiral test conditions: Daicel Chiralpak AS-H (25cm), n-hexane/isopropanol=80/20, 1.0mL/min ^-1 , λ=220nm, t _R (major) = 24.12 min, t _R (minor) = 36.27 min.

P9: (4aS, 8aS)-8a--(3-methylphenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)- Ketone

P9: (4aS, 8aS)-8a-m-tolyl-2, 3, 4a, 5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

White solid, 91% yield, 91% ee [75% yield, 96% ee (ethyl acetate/petroleum ether, recrystallized)].Analytical data for P9 (96% ee): [α] _D ²⁰ =+155.5° (c=1.1, CHCl ₃ ). Mp=113-114°C. ¹ H NMR (300MHz, CDCl ₃ ) δ2.37(s, 3H), 2.46(d, J=3.0Hz, 2H), 3.83-3.91( m, 3H), 4.01-4.06(m, 2H), 6.48(d, J=10.5Hz, 1H), 6.77(dd, J=3.0, 10.5Hz, 1H), 7.16(d, J=6.9Hz, 1H ), 7.25-7.37 (m, 3H); ); ¹³ C NMR (75MHz, CDCl ₃ ) δ21.5, 41.3, 62.8, 66.3, 76.9, 79.3, 123.8, 127.3, 128.4, 129.5, 132.8, 138.3, 138.4, 148.9, 196.6cm ^-1 ; IR(KBr) 2958, 2921, 2866, 1689, 1608, 1404, 1206, 1121, 1111, 1002, 791, 706, 691, 661; HRMS(EI): calculated value of high-resolution mass spectrum C ₁₅ H ₁₆ O ₃ : 244.1099. Measured value: 244.1101; chiral test conditions: Daicel Chiralpak AS-H (25cm), n-hexane/isopropanol=80/20, 1.0mL/min ^-1 , λ=220nm, t _R (major) = 12.22 min, t _R (minor) = 19.61 min.

P10: (4aS,8aS)-8a-(2-methylphenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

P10: (4aS, 8aS)-8a-o-tolyl-2, 3, 4a, 5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

White solid, 92% yield, 95% ee. Analytical data for P10: [α] _D ²⁰ = +66.6° (c = 1.0, CHCl ₃ ). Mp = 107-108°C. ¹ H NMR (300MHz, CDCl ₃ ) δ2.34-2.52(m, 2H), 2.75(s, 3H), 3.79-3.88(m, 2H), 3.97-4.06(m, 2H), 4.49-4.51(m, 1H), 6.49(d, J =10.2Hz, 1H), 6.79(dd, J=3.0, 10.2Hz, 1H), 7.12-7.15(m, 1H), 7.24-7.32(m, 3H); ¹³ C NMR (75MHz, CDCl ₃ ) δ22. 8, 41.6, 62.4, 65.6, 75.0, 78.5, 125.70, 128.0, 128.8, 132.7, 133.8, 135.3, 137.8, 149.7, 196.7; 1086, 1001, 977, 921, 752, 725, 687cm ^-1 ; HRMS (EI): calculated value of high resolution mass spectrum C ₁₅ H ₁₆ O ₃ : 244.1099. Measured value: 244.1102. Chiral test conditions: Daicel ChiralpakAS-H ( 25 cm), n-hexane/isopropanol=80/20, 1.0 mL/min ^-1 , λ=220 nm, t _R (major)=19.98 min, t _R (minor)=31.44 min.

P11: (4aS, 8aS)-8a-(3,5-dimethylphenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH )-ketone

P11: (4aS, 8aS)-8a-(3,5-dimethylphenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

White solid, 81% yield, 90% ee. Analytical data for P11: [α] _D ²⁰ = +165.2° (c = 1.0, CHCl ₃ ). Mp = 130-131 °C. ¹ H NMR (300 MHz, CDCl ₃ ) δ2.32(s, 6H), 2.46(d, J=2.1Hz, 2H), 3.82-3.91(m, 3H), 4.04-4.06(m, 2H), 6.47(d, J=10.5Hz, 1H) , 6.76 (dd, J=3.0, 10.5Hz, 1H), 6.98 (s, 1H), 7.14 (s, 2H); ¹³ C NMR (75MHz, CDCl ₃ ) δ21.4, 41.4, 62.8, 66.3, 76.9, 79.3, 124.4, 130.4, 132.7, 138.2, 138.4, 149.0, 196.7; 854, 807, 703, 679cm ^-1 ; HRMS (EI): Calculated value of high-resolution mass spectrum C ₁₆ H ₁₈ O ₃ : 258.1256. Measured value: 258.1254. Chiral test conditions: Daicel Chiralpak AS-H (25cm), n-hexane /isopropanol=80/20, 1.0 mL/min ⁻¹ , λ=220 nm, t _R (major)=8.94 min, t _R (minor)=15.36 min.

P12: (4aS,8aS)-8a-(3,5-bistrifluoromethylphenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6 (8aH)-ketone

P12: (4aS, 8aS)-8a-(3,5-bis(trifluoromethyl)phenyl)-2,3,4a,5-tetrahydrobenzo[b][1,4]dioxin-6(8aH)-one

Pale yellow oil, 93% yield, 88% ee. Analytical data for P12: [α] _D ²⁰ =+94.3° (c=1.0, CHCl ₃ ). ¹ H NMR (400MHz, CDCl ₃ ) δ2.39-2.58 (m, 2H), 3.91-3.98(m, 4H), 4.08-4.12(m, 1H); 6.58(d, J=10.4Hz, 1H), 6.74(dd, J=2.4, 10.4Hz, 1H), 7.90(s, 1H), 8.01(s, 2H); ¹³ C NMR (100MHz, CDCl ₃ ) δ40.9, 62.8, 66.3, 76.3, 78.9, 122.8(m), 123.0(q, J=272.9), 127.2 (m), 132.1 (q, J=33.5Hz), 134.2, 141.6, 146.5, 195.2; ¹⁹ F NMR (282MHz, CDCl ₃ ) δ-63.2; IR (KBr) 2965, 2924, 2869, 1698, 1625, 1464m 1374, 1279, 1124, 1001, 897, 844, 798, 706, 682, 673cm ^-1 ; HRMS (EI): calculated value of high resolution mass spectrum: C ₁₆ H ₁₂ O ₃ F ₆ : 366.0691. Measured value: 366.0694. Performance test conditions: Daicel Chiralpak AS-H (25cm), n-hexane/isopropanol=80/20, 1.0mL/min ^-1 , λ=220nm, t _R (major)=7.15min, t _R (minor)= 12.57min.

Embodiment 3: the conversion of oxa-Michael product P4

P13: (4aS, 8aS)-8a-Phenylhexahydrobenzo[b][1,4]dioxin-6(7H)-one

P13: (4aS, 8aS)-8a-phenylhexahydrobenzo[b][1,4]dioxin-6(7H)-one

Under argon protection, compound P4 (23.0mg, 0.1mmol), methanol (2mL), 10% palladium carbon (2.3mg) were added to a dry reaction tube. After hydrogen replacement three times, react at room temperature under 1 atmosphere to Raw material disappears. The reaction solution was filtered through celite and washed with methanol. The solvent was spun off under reduced pressure, and the residue was separated by plate chromatography to obtain product P13 (19.7 mg, 85% yield, 99% ee). the

Analytical data for P13: [α] _D ²⁰ = +68.5° (c = 0.5, CHCl ₃ ). Mp = 90-91°C. ¹ HNMR (300MHz, CDCl ₃ ) δ1.95-1.98 (m, 1H), 2.29 -2.36(m, 1H), 2.59-2.71(m, 3H), 3.08(dd, J=7.2, 14.4Hz, 1H), 3.56-3.68(m, 1H), 3.71-3.80(m, 2H), 3.96 -4.02 (m, 1H), 4.60 (t, J=6.0Hz, 1H), 7.35-7.46 (m, 3H), 7.56-7.59 (m, 2H); ¹³ C NMR (75MHz, CDCl ₃ ) δ32.1 , 37.2, 42.3, 60.6, 61.9, 74.6, 74.8, 126.4, 128.0, 128.8, 141.2, 208.6; , 901, 760, 705, 643, 537cm ^-1 ; HRMS (EI): calculated value of high-resolution mass spectrum C ₁₄ H ₁₆ O ₃ : 232.1103. Measured value: 232.1099. Chiral test conditions: Daicel ChiralpakAS-H (25cm), n-hexane/isopropanol = 80/20, 1.0 mL/min ^-1 , λ = 220 nm, t _R (major) = 23.56 min, t _R (minor) = 36.30 min.

P14: (4aS,8aS)-8a-Phenyl-2,3,4a,5,6,8a-Hexahydrobenzo[b][1,4]dioxin

P14: (4aS, 8aS)-8a-phenyl-2, 3, 4a, 5, 6, 8a-hexahydrobenzo[b][1,4]dioxine

Add compound P4 (54.0mg, 0.235mmol), methanol (3mL) and cerium trichloride (106.0mg, 0.285mmol) into a dry reaction tube, cool to 0°C, add sodium borohydride (18.0mg, 0.285mmol ). After reacting at 0 °C for 0.5 h, it was quenched with water and extracted with ethyl acetate (3 x 10 mL). The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was spun off under reduced pressure to obtain the product alcohol, which was directly used in the next reaction without purification. the

The compound sodium hydrogen (18.0 mg, 0.75 mmol) and tetrahydrofuran (3 mL) were sequentially added into a dry reaction tube, and a solution of the above product alcohol in tetrahydrofuran (3 mL) was added dropwise to the above system at room temperature. After reacting at room temperature for 30 minutes, carbon disulfide (90.0 mg, 1.18 mmol) was added, and after the reaction was continued for 1 hour, methyl iodide (64 μL, 1.04 mmol) was added. After reacting at room temperature for 3 hours, quenched with saturated sodium bicarbonate solution, extracted with ethyl acetate, combined organic phases, dried over anhydrous sodium sulfate, and concentrated. The residue was separated by column chromatography (ethyl acetate:petroleum ether=1:5) to obtain the compound (50.3 mg, 67% yield in two steps). The above product was dissolved in dry toluene (4 mL), heated to reflux under the protection of argon, and a toluene solution of tributyltin hydride (102 μL, 0.37 mmol) and azobisisobutyronitrile (5.0 mg, 0.03 mmol) was added dropwise ( 3mL). After reflux for 5 hours, cool to room temperature, remove the solvent under reduced pressure, and purify the residue by column chromatography (ethyl acetate/petroleum ether, 1:10) to obtain compound P14 (30.2 mg, 87% yield, 99% ee) . the

Analytical data for P14: [α] _D ²⁰ =+127.3° (c=1.0, CHCl ₃ ). ¹ H NMR (400 MHz, CDCl ₃ ) δ1.53-1.61 (m, 1H), 1.66-1.73 (m, 1H ), 1.95-2.03(m, 1H), 2.23-2.33(m, 1H), 3.69-3.73(m, 2H), 3.80-3.92(m, 2H), 3.99-4.06(m, 1H), 5.59-5.63 (m, 1H), 6.26-6.31 (m, 1H), 7.26-7.35 (m, 3H), 7.55-7.58 (m, 2H); ¹³ C NMR (75MHz, CDCl ₃ ) δ20.8, 24.4, 61.9, 66.4, 76.4, 76.5, 127.5, 127.6, 127.6, 127.9, 132.9, 143.2; IR (KBr) 2955, 2929, 2858, 1491, 1447, 1252, 1123, 1100, 1026, 946, 908, 757, 700cm ^-1 ; HRMS (EI): Calculated value of high-resolution mass spectrum C ₁₄ H ₁₆ O ₃ : 216.1157. Measured value: 216.1150. Chiral test conditions: Daicel Chiralcel OJ-H (25cm), n-hexane/isopropanol=70/30, 1.0 mL/min ^-1 , λ=220nm, t _R (major)=13.61 min, t _R (minor)=34.86 min.

Embodiment 4: the asymmetric synthesis of long tube pseudojasmonin (C, D, F)

Long tube pseudo-jasmonin F

Add p-hydroxyphenethyl alcohol 2 (276mg, 2mmol) and water (32mL) in sequence to a 250mL reaction flask, stir and dissolve at room temperature. Slowly add potassium persulfate (9.8g, 16mmol) and sodium bicarbonate (4.2g, 50 mmol), reacted at room temperature until the raw materials disappeared, quenched with water, extracted with ethyl acetate, combined organic phases, dried over anhydrous sodium sulfate, filtered and concentrated. The residue was purified by plate chromatography (ethyl acetate:petroleum ether=2:1) to obtain compound P15 (130 mg, 38% yield). ¹ H NMR (300MHz, D ₂ O) δ1.98(t, J=6.9Hz, 2H), 3.55(t, J=6.9Hz, 2H), 6.34(d, J=9.9Hz, 2H), 7.09( d, J=9.9Hz, 2H).

分子筛(150mg)。在室温下反应2小时，经硅藻土过滤，二氯甲烷洗涤。向上述二氯甲烷滤液中加入(亚磷酸三苯酯(140mg，0.45mmol)。在室温下反应0.5h，减压旋除溶剂，残余 物经板层析纯化(乙酸乙酯∶石油醚＝2∶1)得长管假茉莉素F(两步共57％产率，80％ee)。  To the dry reaction tube, add the above product P15 (51.0 mg, 0.3 mmol), CH ₂ Cl ₂ (6 mL), chiral phosphoric acid catalyst (22.8 mg, 10 mol%) and activated

Molecular sieves (150mg). React at room temperature for 2 hours, filter through celite, and wash with dichloromethane. Add (triphenyl phosphite (140 mg, 0.45 mmol) to the above dichloromethane filtrate. React at room temperature for 0.5 h, remove the solvent under reduced pressure, and purify the residue by plate chromatography (ethyl acetate:petroleum ether=2 : 1) to obtain long-tubular pseudojasmonin F (a total of 57% yield in two steps, 80% ee).

Analytical data for long tubular pseudojasmonin F: [α] _D ²⁰ = +29 ° (c = 0.2, CH ₃ OH), [literature (Wenderski, TA; Huang, SL; Pettus, TRRJOrg.Chem.2009, 74, 4104-4109): [α] _D ²⁰ = +59° (c = 1.0, CH ₃ OH)]. ¹ H NMR (300 MHz, CDCl ₃ ) δ 2.10-2.31 (m, 2H), 2.48-2.74 (m , 2H), 3.80(br, 1H), 3.85(dd, J=8.4, 15.0Hz, 1H), 3.99(dd, J=8.4, 15.0Hz, 1H), 4.15(t, J=4.5Hz, 1H) , 5.92 (d, J=9.9Hz, 1H), 6.71 (d, J=9.9Hz, 1H); ¹³ C NMR (75MHz, CDCl ₃ ) δ39.3, 39.9, 66.2, 75.1, 81.2, 128.3, 148.7, 197.6; chiral test conditions: Daicel Chiralpak IC (25cm), n-hexane/isopropanol=70/30, 0.8mL/min ^-1 , λ=220nm, t _R (minor)=8.64min, t _R (major) = 9.63 min.

长管假茉莉素C 

long tube pseudojasmonin C

Under the protection of argon, add long-tube pseudojasmonin F (30.3 mg, 0.2 mmol), methanol (2 mL), and 10% palladium on carbon (6.0 mg) to the dry reaction tube in sequence. It was replaced by hydrogen three times, and reacted at room temperature under 1 atmospheric pressure until the raw materials disappeared. Filtrated through diatomaceous earth, and washed with methanol, the solvent was spun off under reduced pressure, and the residue was purified by plate chromatography (ethyl acetate:petroleum ether=2:1) to obtain the product long tube pseudojasmonin C (94% yield, 81 %ee). the

Analytical data for long tube pseudojasmonin C: [α] _D ²⁰ = -50.0° (c = 1.0, CH ₃ OH), [literature (Wenderski, TA; Huang, SL; Pettus, TRRJOrg.Chem.2009, 74, 4104-4109): [α] _D ²⁰ = -79° (c = 0.1, CH ₃ OH)]. ¹ H NMR (300 MHz, CDCl ₃ ) δ 2.09-2.13 (m, 4H), 2.22-2.32 (m , 1H), 2.45-2.61 (m, 3H), 2.71-2.78 (m, 1H), 3.87-3.99 (m, 3H); ¹³ CNMR (75MHz, CDCl ₃ ) δ33.3, 35.0, 40.4, 42.3, 65.9 , 77.3, 83.4, 210.4; chiral test conditions: chiral GC analysis (Rt-βDEX 30m×0.25mm×0.25um) 60℃-180℃, 5℃/min, 12psi)t _R (major) = 51.91min, t _R (minor) = 54.49 min.

长管假茉莉素D 

long tube fake jasmonin D

分子筛(150mg).在室温下反应2小时后，滴加入苄基三甲基氢氧化铵(40％)的甲醇溶液(30μL).室温下反应30分钟后，经硅藻土过滤，二氯甲烷洗涤，减压旋除溶剂得环氧化合物(含有手性磷酸催化剂)，无需纯化，直接用于下一步反应。  Add compound P15 (51.0mg, 0.3mmol), dichloromethane (6mL), chiral phosphoric acid catalyst (22.8mg, 10mol%) and activated

Molecular sieves (150 mg). After reacting at room temperature for 2 hours, add dropwise a methanol solution (30 μL) of benzyltrimethylammonium hydroxide (40%). After reacting at room temperature for 30 minutes, filter through diatomaceous earth, dichloromethane After washing, the solvent was removed under reduced pressure to obtain an epoxy compound (containing a chiral phosphoric acid catalyst), which was directly used in the next reaction without purification.

The above epoxy compound, tetrahydrofuran (4 mL), ethanol (1.6 mL), water (1.6 mL) and saturated sodium bicarbonate (0.4 mL) were sequentially added to the reaction tube, and freshly prepared aluminum amalgam was added at room temperature. The reaction was stirred vigorously until the starting material disappeared. Filter through celite, wash with ethanol, extract the filtrate with ethyl acetate, and combine the organic phases. Dry over anhydrous sodium sulfate, filter, and spin off the solvent under reduced pressure. The residue is purified by column chromatography (ethyl acetate) to obtain the compound jasmonin D (13.8 mg, 27% yield in three steps). the

Analytical data for compound P16 (80%ee): ¹ H NMR (300MHz, CDCl ₃ ) δ2.12-2.19 (m, 1H), 2.28-2.34 (m, 1H), 2.67-2.97 (m, 2H), 3.98 -4.03(m, 2H), 4.56(t, J=5.1Hz, 1H), 6.17(d, J=10.2Hz, 1H), 6.84(d, J=10.2Hz, 1H), 8.56(br, 1H) ; ¹³ CNMR (100MHz, CDCl ₃ ) δ36.4, 41.2, 66.1, 78.8, 86.6, 130.7, 146.7, 197.2; chiral test conditions: Daicel Chiralpak AD-H (25cm), n-hexane/isopropanol=80/ 20, 1.0 mL/min ^-1 , λ = 220 nm, t _R (major) = 6.08 min, t _R (minor) = 7.01 min.

Analytical data for long tubular pseudojasmonin D: [α] _D ²⁰ = -63° (c = 0.2, CH ₃ OH), [literature [α] _D ²⁰ = -38° (c = 0.5, CH ₃ OH); Wenderski, TA; Huang, SL; Pettus, TRRJOrg.Chem.2009, 74, 4104-4109.]. ¹ H NMR (400MHz, CDCl ₃ ) δ2.12-2.16(m, 2H), 2.63-2.56(m, 3H), 2.77(br, 1H), 2.92(dd, J=3.6, 12.6Hz, 1H), 2.94(br, 1H), 3.89-3.93(m, 1H), 3.99-4.02(m, 2H), 4.13 (br, 1H); ¹³ C NMR (75 MHz, CDCl ₃ ) δ 38.7, 41.6, 42.2, 66.1, 70.9, 78.6, 82.7, 207.4.

Claims (8)

1. A furan compound has the following structural formula:

wherein ^R1 is selected from H wherein ^R2 is selected from OOH, wherein X is selected from _CH2 . 2. a synthetic method of furan compound as claimed in claim 1, is characterized in that in-78 ℃ to 100 ℃ and organic solvent, with cyclohexadienone derivatives as raw material, with chiral phosphoric acid as catalyzer to carry out Intramolecular oxa-Michael reaction for 30 minutes to 48 hours, the molar ratio of the cyclohexadienone derivative to chiral phosphoric acid is 1:0.01-0.5; wherein, the structural formula of the cyclohexadienone derivative is as follows :

The structural formula of the catalyst is

or

Wherein R ¹ , R ² or X are as described in claim 1; R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ or R ¹² are randomly selected from H, C1-C16 alkyl, triarylsilyl, aryl; The aryl mentioned above is naphthyl, anthracenyl or phenanthrenyl. 3. the method for the synthetic furan compound as claimed in claim 2 is characterized in that described organic solvent is benzene, carbon tetrachloride, sherwood oil, tetrahydrofuran (THF), dimethylformamide, ether, methylene dichloride, chloroform , toluene, xylene, cyclohexane, n-hexane, n-heptane, dioxane or acetonitrile. the 4. the method for synthetic furan compound as claimed in claim 2 is characterized in that gained product is separated and purified through recrystallization, thin-layer chromatography, column chromatography or vacuum distillation. the 5. a purposes of furan compound as claimed in claim 1, is characterized in that being used for preparing following structural formula

Compounds: Jasmolin F, Jasmolin C, or Jasmolin D. the 6. purposes as claimed in claim 5, it is characterized in that in organic solvent and at room temperature, described furan compound and reducing agent react 1-72 hour and obtain long-tube pseudojasmonin F compound, described furan compound and The molar ratio of the reducing agent is 1:1-5; the reducing agent is sodium sulfite, sodium thiosulfate, triphenyl phosphite or triphenylphosphine. the 7. purposes as claimed in claim 5, it is characterized in that in organic solvent and at room temperature, described furan compound and reducing agent react 1-72 hour and obtain long-tube pseudojasmonin F compound, described furan compound and The molar ratio of reducing agent is 1: 1-5; Described reducing agent is sodium sulfite, sodium thiosulfate, triphenyl phosphite or triphenyl phosphorus; In organic solvent and at room temperature, described long tube pseudo The jasmonin F compound is hydrogenated on palladium carbon for 1-72 hours to obtain the long-tubular pseudojasmone C compound, and the long-tubular pseudojasmone F compound and palladium-carbon 1: 0.01-0.2. the 8. purposes as claimed in claim 5, it is characterized in that in organic solvent and at room temperature, described furan compound reacts 1-72 hour with potassium carbonate, sodium carbonate or benzyl trimethyl ammonium hydroxide, then with The reducing agent is reacted for 1-72 hours to obtain the long-tube pseudojasmonin D compound; the reducing agent is triethylaluminum borohydride, aluminum amalgam or lithium aluminum hydride; the furan compound is mixed with potassium carbonate, sodium carbonate or The molar ratio of benzyltrimethylammonium hydroxide is 1:0.1-0.5; the molar ratio of the furan compound to the reducing agent is 1:1-10. the