CN102875278B - 一种合成光学活性的2-(2’, 3’-联烯基)丙二酸酯的方法 - Google Patents
一种合成光学活性的2-(2’, 3’-联烯基)丙二酸酯的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title abstract 5
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- -1 cinnamyl palladium chloride Chemical compound 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 15
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 claims description 14
- ZNORAFJUESSLTM-UHFFFAOYSA-N [4-[5-bis(3,5-ditert-butyl-4-methoxyphenyl)phosphanyl-1,3-benzodioxol-4-yl]-1,3-benzodioxol-5-yl]-bis(3,5-ditert-butyl-4-methoxyphenyl)phosphane Chemical compound C1=C(C(C)(C)C)C(OC)=C(C(C)(C)C)C=C1P(C=1C(=C2OCOC2=CC=1)C=1C(=CC=C2OCOC2=1)P(C=1C=C(C(OC)=C(C=1)C(C)(C)C)C(C)(C)C)C=1C=C(C(OC)=C(C=1)C(C)(C)C)C(C)(C)C)C1=CC(C(C)(C)C)=C(OC)C(C(C)(C)C)=C1 ZNORAFJUESSLTM-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000002690 malonic acid derivatives Chemical class 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000006717 asymmetric allylation reaction Methods 0.000 description 2
- 229960003328 benzoyl peroxide Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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Abstract
一种合成光学活性的2-(2’,3’-联烯基)丙二酸酯的方法，通过各种取代的2,3-联烯醇醋酸酯在肉桂基氯化钯和(RorS)-DTBM-SEGPHOS的催化下得到各种取代的光学活性的2-(2’,3’-联烯基)丙二酸酯，本方法操作简单，原料和试剂易得，反应具有较高的产率，较高的ee值，产物易分离纯化，适用于合成各种取代的光学活性的2-(2’,3’-联烯基)丙二酸酯的合成。
Description
技术领域
本发明涉及一种合成光学活性的2-(2’,3’-联烯基)丙二酸酯的方法，具体地说，是通过2, 3-联烯醇醋酸酯和丙二酸二乙酯的反应，以较好的产率和高对映选择性地合成光学活性的2-(2’, 3’-联烯基)丙二酸酯的方法。
背景技术
联烯化学的发展为有机合成化学领域做出了重大的贡献，特别是光学活性的联烯化合物，更是得到了广泛的应用。另外，丙二酸酯在有机合成中也是一种重要的中间体。目前，通过不对称烯丙基化的方法合成轴手性的联烯基丙二酸酯已有不少报道，(ref. a) M. Ogasawara, H. Ikeda, T. Nagano, T. Hayashi, J. Am. Chem. Soc. 2001, 123, 2089-2090; b) M. Ogasawara, K. Ueyama, T. Nagano, Y. Mizuhata, T. Hayashi, Org. Lett. 2003, 5, 217-219; c) M. Ogasawara, T. Nagano, T. Hayashi, J. Org. Chem. 2005, 70, 5764-5767; d) M. Ogasawara, H. L. Ngo, T. Sakamoto, T. Takahashi, W. Lin, Org. Lett. 2005, 7, 2881-2884; e) M. Ogasawara, Y. Ge, K. Uetake, T. Takahashi, Org. Lett. 2005, 7, 5697-5700; f) Y. Imada, K. Ueno, K. Kutsuwa, S.-I. Murahashi, Chem. Lett. 2002, 140-141; g) B. M. Trost, D. R. Fandrick, D. C. Dinh, J. Am. Chem. Soc. 2005, 127, 14186-14187; h) T. Nemoto, M. Kanematsu, S. Tamura, Y. Hamadaa, Adv. Synth. Catal. 2009, 351, 1773-1778.）但是对于含有中心手性的联烯基丙二酸酯化合物 2，则还没有文献报道。
发明内容
本发明的目的就是提供一种通过钯和手性配体催化的2，3-联烯醇醋酸酯和丙二酸二乙酯的不对称反应来合成光学活性的2-(2’, 3’-联烯基)丙二酸酯的方法，本发明的具体技术方案如下：
本发明是一种合成光学活性的2-(2’,3’-联烯基)丙二酸酯的方法，即通过2, 3-联烯醇醋酸酯和丙二酸二乙酯的在肉桂基氯化钯和(R or S)-DTBM-SEGPHOS的催化下反应，以较好的产率和高对映选择性地得到光学活性的2-(2’, 3’-联烯基)丙二酸酯的方法，反应式如下：
R = 烷基，其中烷基为C n H2n+1(n = 2-9)，或C n H2nFG (其中FG = Cl, CN, OH, OAc, 烯基或者是三甲基硅基乙炔基, n = 3-8)，其步骤是：
（1） 在氮气保护下，加入碳酸钾，然后将[Pd(pi-cinnamyl)Cl]2，(R or S)-DTBM-SEGPHOS，2, 3-联烯醇醋酸酯，无水乙醚，丙二酸二乙酯，无水乙醚和水依次加入，一定温度下反应至完毕；
（2） 步骤（1）反应完全后，硅胶短柱过滤，乙醚洗涤；
（3） 浓缩，柱层析，获得光学活性的2-(2’, 3’-联烯基)丙二酸酯。
本发明所述的2中R为烷基或带有各种官能团的烷基。
本发明所述的2, 3-联烯醇醋酸酯1：丙二酸二乙酯：[Pd(pi-cinnanyl)Cl]2: (R or S)-DTBM-SEGPHOS：K2CO3：水：乙醚 = 1毫摩尔: 1~4毫摩尔: 0.01~0.1毫摩尔: 0.01~0.4毫摩尔: 1~4毫摩尔: 0.5~5毫摩尔: 2~20毫升。
本发明具有以下优点：
1）反应条件相对简单，室温反应；2）产物易分离纯化；3）反应具有良好的产率和较高的对映选择性。
本发明创新点在于首次用不对称烯丙基化的方法合成了光学活性的2-(2’, 3’-联烯基)丙二酸酯。
本发明所得到的相应的2-(2’, 3’-联烯基)丙二酸酯的产率为71-84%， ee值为92-96%。
具体实施方式
以下实施例有助于理解本发明，但不限于本发明的内容。
实施例1
在氮气保护下，将碳酸钾，[Pd(pi-cinnamyl)Cl]2，(R)-DTBM-SEGPHOS，4,5-己二烯-3-醇醋酸酯，乙醚，丙二酸二乙酯，乙醚及水依次加入到反应管中，室温搅拌24小时，薄层层析跟踪原料消失后，硅胶短柱过滤，50 mL乙醚洗涤，浓缩，柱层析，得产物(S)-2-(4’,5’-己二烯-3’-基)丙二酸二乙酯 90.2 mg, 产率为75%，93%ee，产物为液体。
HPLC condition: Chiralpak PA-2 column; eluent, n-hexane/i-PrOH = 97/3; rate, 0.5 mL/min; λ = 220 nm; tR 14.6 min (major), 15.7 min (minor); [α]20 D = +18.1 (c = 0.99, CHCl3); 1H NMR (300 MHz, CDCl3) δ 5.17-5.01 (m, 1 H, =CH), 4.75-4.61 (m, 2 H, =CH2), 4.25-4.07 (m, 4 H, 2 × CH2), 3.35 (d, J = 8.7 Hz, 1 H, CH), 2.79-2.63 (m, 1 H, CH), 1.60-1.15 (m, 8 H, CH2 + 2 × CH3), 0.90 (t, J = 7.4 Hz, 3 H, CH3); 13C NMR (75 MHz, CDCl3) δ 208.4, 168.3, 168.1, 90.3, 75.6, 61.2, 61.1, 56.6, 40.3, 25.5, 14.0, 11.4; IR (neat) ν (cm-1) 2979, 2937, 2872, 1958, 1751, 1732, 1464, 1369, 1258, 1177, 1097, 1035; MS (EI) m/z (%) 240 (M+, 36.71), 79 (100); HRMS calcd for C13H20O4 (M+): 240.1362, found: 240.1369.
实施例2
按实施例1所述的方法，不同的是所用底物为：1,2-壬二烯-4-醇醋酸酯 (90.5 mg, 0.5 mmol), 丙二酸二乙酯 (160.3 mg, 1.0 mmol), [Pd(pi-cinnamyl)Cl]2 (6.4 mg, 0.0125 mmol), (R)-DTBM-SEGPHOS (35.4 mg, 0.03 mmol), K2CO3 (138.2 mg, 1.0 mmol) 及 H2O (9 μL, 0.5 mmol) 在 5 mL乙醚中得到(S)- 2-(1’,2’-壬二烯-4’-基)丙二酸二乙酯109.6 mg，产率为78%，ee值为95%，产物为液体。
HPLC conditions: Chiralpak IC column; eluent, n-hexane/i-PrOH = 99/1; rate, 0.6 mL/min; λ = 214 nm; tR 16.4 min (major), 18.0 min (minor)；[α]20 D = +17.4 (c = 1.01, CHCl3); 1H NMR (300 MHz, CDCl3) δ 5.16-5.02 (m, 1 H, =CH), 4.74-4.60 (m, 2 H, =CH2), 4.26-4.08 (m, 4 H, 2 × CH2), 3.34 (d, J = 9.0 Hz, 1 H, CH), 2.86-2.69 (m, 1 H, CH), 1.52-1.12 (m, 14 H, 4 × CH2 + 2 × CH3), 0.84 (t, J = 6.8 Hz, 3 H, CH3); 13C NMR (75 MHz, CDCl3) δ 208.4, 168.3, 168.1, 90.7, 75.6, 61.2, 61.1, 56.9, 38.8, 32.5, 31.5, 26.5, 22.4, 14.0, 13.9; IR (neat) ν (cm-1) 2980, 2958, 2932, 2859, 1957, 1732, 1465, 1369, 1308, 1247, 1175, 1036; MS (EI) m/z (%) 282 (M+, 6.09), 211 (100); HRMS calcd for C16H26O4 (M+): 282.1831, found: 282.1837.
实施例3
按实施例1所述的方法，不同的是所用底物为：1,2,13-十四碳三烯-4-醇醋酸酯 (125.8 mg, 0.5 mmol), 丙二酸二乙酯 (158.0 mg, 1.0 mmol), [Pd(pi-cinnamyl)Cl]2 (6.6 mg, 0.0127 mmol), (R)-DTBM-SEGPHOS (35.4 mg, 0.03 mmol), K2CO3 (138.0 mg, 1.0 mmol) 及 H2O (9 μL, 0.5 mmol) 在 5 mL Et2O中得到(S)- 2-(1’,2’,13’-十四碳三烯-4’-基)丙二酸二乙酯124.9 mg, 产率为71%, ee 值为93%, 产物为液体。
HPLC condition: Chiralpak IC column; eluent, n-hexane/i-PrOH = 99/1; rate, 0.6 mL/min; λ = 214 nm; tR 16.8 min (major), 17.7 min (minor); [α]20 D = + 12.9 (c = 0.86, CHCl3); 1H NMR (300 MHz, CDCl3) δ 5.86-5.67 (m, 1 H, =CH), 5.14-5.02 (m, 1 H, =CH), 5.00-4.83 (m, 2 H, =CH2), 4.70-4.61 (m, 2 H, =CH2), 4.24-4.07 (m, 4 H, 2 × CH2), 3.33 (d, J = 8.7 Hz, 1 H, CH), 2.85-2.68 (m, 1 H, CH), 1.99 (q, J = 6.9 Hz, 2 H, CH2), 1.51-1.06 (m, 20 H, 7 × CH2 + 2 × CH3); 13C NMR (75 MHz, CDCl3) δ 208.3, 168.3, 168.0, 139.0, 114.0, 90.6, 75.6, 61.2, 61.1, 56.8, 38.8, 33.7, 32.5, 29.33, 29.28, 29.2, 29.0, 28.8, 26.8, 14.0; IR (neat) ν (cm-1) 3076, 2980, 2927, 2855, 1957, 1732, 1640, 1464, 1368, 1299, 1251, 1176, 1035; MS (EI) m/z (%) 350 (M+, 5.25), 211 (100); HRMS calcd for C21H34O4 (M+): 350.2457, found: 350.2454.
实施例4
按实施例1所述的方法，不同的是所用底物为：9-羟基-1,2-壬二烯-4-醇醋酸酯 (98.4 mg, 0.5 mmol), 丙二酸二乙酯 (161.0 mg, 1.0 mmol), [Pd(pi-cinnamyl)Cl]2 (6.5 mg, 0.0125 mmol), (R)-DTBM-SEGPHOS (35.5 mg, 0.03 mmol), K2CO3 (138.0 mg, 1.0 mmol) 及H2O (9 μL, 0.5 mmol) 在5 mL Et2O 中得到 (S)-2-(9’-羟基-1’,2’-壬二烯-4’-基)丙二酸二乙酯 124.8 mg, 产率为84%, ee值为96%, 产物为液体。
HPLC condition: Chiralpak IC column; eluent, n-hexane/i-PrOH = 90/10; rate, 1.0 mL/min; λ = 214 nm; tR 20.5 min (major), 22.5 min (minor); [α]20 D = + 15.3 (c = 1.01, CHCl3); 1H NMR (300 MHz, CDCl3) δ 5.11-4.98 (m, 1 H, =CH), 4.73-4.58 (m, 2 H, =CH2), 4.24-4.01 (m, 4 H, 2 × CH2), 3.55 (t, J = 6.8 Hz, 2 H, CH2), 3.31 (d, J = 8.7 Hz, 1 H, CH), 2.82-2.66 (m, 1 H, CH), 2.10 (bs, 1 H, OH), 1.60-1.09 (m, 14 H, 4 × CH2 + 2 × CH3); 13C NMR (75 MHz, CDCl3) δ 208.2, 168.3, 168.0, 90.4, 75.7, 62.5, 61.2, 61.1, 56.8, 38.6, 32.38, 32.35, 26.6, 25.3, 13.9; IR (neat) ν (cm-1) 3418, 2983, 2936, 2861, 1957, 1732, 1464, 1447, 1369, 1307, 1251, 1177, 1153, 1096, 1034; MS (EI) m/z (%) 298 (M+, 4.23), 211 (100); HRMS calcd for C16H26O5 (M+): 298.1780, found: 298.1778.
实施例5
按实施例1所述的方法，不同的是所用底物为：9-乙酰氧基-1,2-壬二烯-4-醇醋酸酯 (120.7 mg, 0.5 mmol), 丙二酸二乙酯(159.0 mg, 1.0 mmol), [Pd(pi-cinnamyl)Cl]2 (6.5 mg, 0.0125 mmol), (R)-DTBM-SEGPHOS (35.6 mg, 0.03 mmol), K2CO3 (137.7 mg, 1.0 mmol) 及 H2O (9 μL, 0.5 mmol) 在 5 mL Et2O 中得到 (S)-2-(9’-乙酰氧基-1’,2’-壬二烯-4’-基)丙二酸二乙酯 142.9 mg, 产率为84%, ee值为 96%, 产物为液体。
HPLC conditions: Chiralpak IC column; eluent, n-hexane/i-PrOH = 92/8; rate, 1.0 mL/min; λ = 214 nm; tR 25.9 min (major), 28.7 min (minor); [α]20 D = + 16.0 (c = 1.06, CHCl3); 1H NMR (300 MHz, CDCl3) δ 5.08-4.98 (m, 1 H, =CH), 4.69-4.55 (m, 2 H, =CH2), 4.19-4.01 (m, 4 H, 2 × CH2), 3.97 (t, J = 6.6 Hz, 2 H, CH2), 3.30 (d, J = 8.7 Hz, 1 H, CH), 2.80-2.65 (m, 1 H, CH), 1.97 (s, 3 H, CH3), 1.62-1.46 (m, 2 H, CH2), 1.46-1.10 (m, 12 H, 3 × CH2 + 2 × CH3); 13C NMR (75 MHz, CDCl3) δ 208.3, 171.0, 168.1, 167.9, 90.4, 75.7, 64.3, 61.2, 61.1, 56.7, 38.6, 32.2, 28.3, 26.5, 25.5, 20.8, 13.9; IR (neat) ν (cm-1) 2980, 2939, 2861, 1957, 1732, 1464, 1444, 1368, 1243, 1177, 1153, 1090, 1035; MS (EI) m/z (%) 340 (M+, 5.68), 43 (100); HRMS calcd for C18H28O6 (M+): 340.1886, found: 340.1883.
实施例6
按实施例1所述的方法，不同的是所用底物为：9-三甲基硅基 -1,2-壬二烯-8-炔-4-醇醋酸酯 (124.9 mg, 0.5 mmol), 丙二酸二乙酯 (159.8 mg, 1.0 mmol), [Pd(pi-cinnamyl)Cl]2 (6.4 mg, 0.0124 mmol), (R)-DTBM-SEGPHOS (35.8 mg, 0.03 mmol), K2CO3 (138.5 mg, 1.0 mmol) 及H2O (9 μL, 0.5 mmol) 在 5 mL Et2O 中得到 (S)- 2-(9’-三甲基硅基 -1’,2’-壬二烯-8’-炔-4’-基)丙二酸二乙酯125.5 mg, 产率为72%, ee值为92% , 产物为液体。
HPLC conditions: Chiralpak IC column; eluent, n-hexane/i-PrOH = 99/1; rate, 0.4 mL/min; λ = 214 nm; tR 20.8 min (major), 21.8 min (minor); [α]20 D = + 8.1 (c = 0.99, CHCl3); 1H NMR (300 MHz, CDCl3) δ 5.16-5.00 (m, 1 H, =CH), 4.73-4.62 (m, 2 H, =CH2), 4.23-4.00 (m, 4 H, 2 × CH2), 3.32 (d, J = 8.7 Hz, 1 H, CH), 2.85-2.67 (m, 1 H, CH), 2.26-2.06 (m, 2 H, CH2), 1.70-1.32 (m, 4 H, 2 × CH2), 1.22 (t, J = 7.2 Hz, 3 H, CH3), 1.21 (t, J = 7.1 Hz, 3 H, CH3), 0.08 (s, 9 H, 3 × CH3); 13C NMR (75 MHz, CDCl3) δ 208.3, 168.1, 167.9, 106.8, 90.3, 84.5, 75.9, 61.2, 61.1, 56.8, 38.4, 31.6, 26.1, 19.6, 14.0, 0.001; IR (neat) ν (cm-1) 2980, 2958, 2899, 2866, 2174, 1957, 1754, 1735, 1447, 1369, 1301, 1249, 1177, 1151, 1096, 1032; MS (EI) m/z (%) 350 (M+, 0.17), 335 (M+ - CH3, 4.85), 73 (100); elemental analysis calcd for C19H30O4Si: C, 65.10; H, 8.63. found: C, 65.19; H, 8.50.
Claims (2)
1.一种合成光学活性的2-(2’,3’-联烯基)丙二酸酯的方法，即通过2, 3-联烯醇醋酸酯和丙二酸二乙酯的在肉桂基氯化钯和(R)-DTBM-SEGPHOS的催化下反应，选择性地得到光学活性的2-(2’, 3’-联烯基)丙二酸酯的方法，反应式如下：
R = 烷基，其中烷基为C n H2n+1, n = 2-9；或C m H2mFG，其中FG = Cl, CN, OH, OAc, 烯基或者是三甲基硅基乙炔基, m = 3-8，其步骤是：
（1） 在氮气保护下，加入碳酸钾，然后将[Pd(pi-cinnamyl)Cl]2，(R)-DTBM-SEGPHOS，2, 3-联烯醇醋酸酯，无水乙醚，丙二酸二乙酯，无水乙醚和水依次加入，一定温度下反应至完毕；
（2） 步骤（1）反应完全后，硅胶短柱过滤，乙醚洗涤；
（3） 浓缩，柱层析，获得光学活性的2-(2’, 3’-联烯基)丙二酸酯。
2.根据权利要求1所述的合成光学活性的2-(2’,3’-联烯基)丙二酸酯的方法，其特征是所述的2, 3-联烯醇醋酸酯1：丙二酸二乙酯：[Pd(pi-cinnamyl)Cl]2: (R)-DTBM-SEGPHOS：K2CO3：水：乙醚 = 1毫摩尔: 1~4毫摩尔: 0.01~0.1毫摩尔: 0.01~0.4毫摩尔: 1~4毫摩尔: 0.5~5毫摩尔: 2~20毫升。
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