CN103755566A - 一种不对称催化合成(s)-2-芳基丙酸酯的新方法 - Google Patents

一种不对称催化合成(s)-2-芳基丙酸酯的新方法 Download PDF

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CN103755566A
CN103755566A CN201410023042.7A CN201410023042A CN103755566A CN 103755566 A CN103755566 A CN 103755566A CN 201410023042 A CN201410023042 A CN 201410023042A CN 103755566 A CN103755566 A CN 103755566A
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CN103755566B (zh
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边庆花
钟江春
毛建友
郑冰
刘飞鹏
王敏
李硕宁
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Abstract

本发明公开了一种钴催化的不对称Kumada交叉偶联反应合成(S)-2-芳基丙酸酯的新方法。该方法开创性地采用不对称催化Kumada交叉偶联的方法，由外消旋的2-卤代丙酸酯与芳基格氏试剂发生Kumada交叉偶联反应直接生成(S)-2-芳基丙酸酯。该方法一步直接得到含手性甲基的(S)-2-芳基丙酸酯，反应产率高，产物光学纯度高。

Description

一种不对称催化合成(S)-2-芳基丙酸酯的新方法
技术领域
背景技术
2-芳基丙酸是一类广泛使用的非甾体抗炎药物,不仅具有良好的解热、消炎和镇痛作用，而且具有毒性低、患者易于耐受等优点。2-芳基丙酸类抗炎药的侧链都具有一个手性碳原子，研究表明：(S)-构型一般比(R)-构型活性强、副作用小（Rubin,A.;Knadler,M.P.;Ho,P.P.K.;Bechtol,L.D.;Wolen,R.L.J.Pharm.Sci.1985,74(1),82–84.；Mayer,J.M.;Testa,B.Drug Fut.1997,22(12),1347–1366.）。(S)-构型是此类非甾体抗炎药物的活性成分。(S)-2-芳基丙酸酯(式1)可以直接一步水解为(S)-2-芳基丙酸，是合成(S)-2-芳基丙酸类非甾体抗炎手性药物的重要中间体。目前，获得(S)-2-芳基丙酸酯主要有外消旋体拆分法、化学剂量不对称合成、酶催化法、不对称催化合成法以及电化学还原偶联法。 
Figure BDA0000458375340000011
(1)外消旋体拆分法主要是外消旋6-甲氧基-2-萘丙酸酯的烯醇式与(S)-手性质子酸的不对称质子化反应（Munoz-Muniz,O.;Juaristi,E.Tetrahedron Lett.2003,44(10),2023–2026.）。 
(2)化学剂量不对称合成主要是三氯化铝催化的芳香烃与(S)-2-磺酰基丙酸酯发生付氏烷基化反应（Piccolo,O.;Azzena,U.;Melloni,G;Delogu,G.;Valoti,E.J.Org.Chem.1991,56(1),183–187.）。 
(3)酶催化法的研究主要是酶催化外消旋芳香酸的不对称酯化反应（Bando,T.;Namba,Y.;Shishido,K.Tetrahedron:Asymmetry1997,8(13),2159–2165.）。 
(4)不对称催化法主要包括苯并四咪唑类催化剂催化的外消旋芳香酸与二-α-萘基甲醇的不对称酯化反应（Shiina,I.;Nakata,K;Ono,K.;Onda,Y.-s.;Itagaki,M.J.Am.Chem.Soc.2010,132(33),11629–11641.），钯催化的酯的不对称芳基化反应（Huang,Z.;Liu,Z.;Zhou,J.S.J.Am.Chem.Soc.2011,133(40),15882–15885.），弱金鸡纳碱催化的酯的不对称烷基化反应（Andrus,M.B.;Harper,K.C.;Christiansen,M.A.;Binkley,M.A.Tetrahedron Lett.2009,50(31),4541–4544），手性季铵盐催化的6-甲氧基-2-萘乙酸酯的不对称烷基化反应（Kumar,S.; Ramachandran,U.Tetrahedron:Asymmetry2005,16(3),647–649.），以及钌催化的芳基烯醇酯的不对称氢化反应（Qiu,L.;Wu,J.;Chan,S.;Au-Yeung,T.T.L.;Ji,J.-X.;Guo,R.;Pai,C.-C.;Zhou,Z.;Li,X.;Fan Q.-H.;Chan,A.S.C.Proc.Natl.Acad.Sci.U S A2004,101(16),5815–5820.） 
(5)电化学还原偶联法主要是镍催化的6-甲氧基萘基溴与2-氯丙酸酯的电化学还原偶联反应（Durandetti,M.;Perichon,J.;Nedelec,J.V.J.Org.Chem.1997,62(23),7914–7915.）。 
虽然关于(S)-2-芳基丙酸酯的不对称合成研究已有一些报道，但仍然存在许多问题，例如需要酶试剂、化学计量的手性试剂、反应条件苛刻，反应步骤繁琐等，因此，研究高效的、对环境友好的、简捷的新的不对称合成方法具有重要的意义。 
发明内容
本发明提供一种钴催化的不对称Kumada交叉偶联反应合成(S)-2-芳基丙酸酯的新方法。该方法开创性地采用不对称催化Kumada交叉偶联的方法，由外消旋的2-卤代丙酸酯与芳基格氏试剂发生Kumada交叉偶联反应生成(S)-2-芳基丙酸酯。该方法一步直接得到含手性甲基的(S)-2-芳基丙酸酯，反应产率高（up to95%），产物光学纯度高（up to97%）。本发明不对称催化合成(S)-2-芳基丙酸酯的合成方法参见式2。 
Figure BDA0000458375340000021
本发明不对称催化合成(S)-2-芳基丙酸酯包括如下步骤。 
(1)使用商品化格氏试剂的制备方法 
氩气保护下，在钴盐和双噁唑啉手性配体的混合溶液中加入外消旋的2-卤代丙酸酯，室温搅拌。降低反应温度后，加入芳基格氏试剂，继续搅拌反应。淬灭反应，萃取干燥，减压浓缩后经硅胶柱色谱纯化，制得(S)-2-芳基丙酸酯。 
(2)使用自制格氏试剂的制备方法 
氩气保护下，在镁粉中加入无水THF和芳基卤，加热回流3h，制得芳基格氏试剂。氩气保护下，在钴盐和双噁唑啉手性配体的混合溶液中加入外消旋的2-卤代丙酸酯，室温搅拌。降低反应温度后，加入自制的芳基格氏试剂，继续搅拌反应。淬灭反应，萃取干燥，减压浓 缩后经硅胶柱色谱纯化，制得(S)-2-芳基丙酸酯。 
下表为利用不对称催化Kumada交叉偶联反应合成(S)-2-芳基丙酸酯类化合物示例。 
表1外消旋溴代丙酸酯与芳基格氏试剂的不对称Kumada交叉偶联反应 
上述反应均在无水四氢呋喃中进行，反应温度为–80℃。上述反应使用的卤代羧酸酯为2-溴丙酸苄酯，钴盐为CoI2，使用的双噁唑啉手性配体结构参见式3。 
Figure BDA0000458375340000032
具体实施方式
实施例1 
(S)-2-苯基丙酸酯3a的合成 
氩气保护下，在干燥的Schlenk瓶中加入CoI2(31.2mg,0.1mmol)，真空干燥2h后，加入无水四氢呋喃（3mL）和双噁唑啉手性配体L1(43.5mg,0.12mmol)，室温下搅拌1h。在混合液中加入外消旋的2-溴苯丙酸苄酯(243.0mg,1.0mmol)，降低反应温度至–80℃，逐滴加入苯基溴化镁(0.47mL,3.0M乙醚溶液,1.4mmol)。在–80℃下继续搅拌反应5h，加 入饱和氯化铵水溶液淬灭反应。反应液用乙醚（15mL×4）萃取，合并有机层，无水硫酸钠干燥，减压浓缩后经硅胶柱色谱纯化（正己烷/乙酸乙酯40:1），得无色油状物(S)-2-苯基丙酸酯3a(228.0mg,产率95%，光学纯度94%)。[α]D 20=+20.9(c1.7,CHCl3);1H NMR(300MHz,CDCl3)δ:7.31–7.21(m,10H),5.14(d,J=12.5Hz,1H),5.06(d,J=12.5Hz,1H),3.77(q,J=7.2Hz,1H),1.52(d,J=7.2Hz,3H);13C NMR(75MHz,CDCl3)δ:174.2,140.3,135.9,128.5,128.4,128.0,127.8,127.5,127.1,66.3,45.5,18.4;HRMS(ESI)calcd for C16H15O2[M-H]+239.1072,found239.1080. 
实施例2 
(S)-间甲基苯基丙酸酯3h的合成 
氩气保护下，在干燥的Schlenk管中加入镁粉(72.9mg,3mmol)和无水THF(2.5mL)，然后加入3-甲基溴苯(85.5mg,0.5mmol)。搅拌反应，小心加热至引发反应，缓慢加入剩余的3-甲基溴苯(256.5mg,1.5mmol)。反应液回流3h，制得灰黑色的3-甲基苯基溴化镁THF溶液。 
氩气保护下，在干燥的Schlenk瓶中加入CoI2(31.2mg,0.1mmol)，真空干燥2h后，加入无水四氢呋喃（3mL）和双噁唑啉手性配体L1(43.5mg,0.12mmol)，室温下搅拌1h。在混合液中加入外消旋的2-溴苯丙酸苄酯(243mg,1.0mmol)，降低反应液温度至–80℃，缓慢滴入自制的3-甲基苯基溴化镁溶液。在–80℃下继续搅拌反应24h，加入饱和氯化铵水溶液淬灭反应。反应液用乙醚（15mL×4）萃取，合并有机层，无水硫酸钠干燥，减压浓缩后经硅胶柱色谱纯化（正己烷/乙酸乙酯80:1），得无色油状物(S)-间甲基苯基丙酸酯3h(183.0mg,产率72%，光学纯度94%)。[α]D 20=+13.1(c1.4,CHCl3);1H NMR(300MHz,CDCl3)δ:7.32–7.05(m,9H),5.14(d,J=12.5Hz,1H),5.07(d,J=12.5Hz,1H),3.74(q,J=7.2,1H),2.32(s,3H),1.50(d,J=7.2Hz,3H);13C NMR(75MHz,CDCl3)δ:174.4,140.3,138.2,136.1,128.5,128.4,128.2,128.0,127.9,124.6,66.3,45.5,21.4,18.5;HRMS(ESI)calcd for C17H17O2[M-H]-:253.1229,found253.1224. 
实施例3 
(S)-2-(2-萘基)丙酸酯3l的合成 
氩气保护下，在干燥的Schlenk瓶中加入CoI2(31.2mg,0.1mmol)，真空干燥2h后，加入无水四氢呋喃（3mL）和双噁唑啉手性配体L1(43.5mg,0.12mmol)，室温下搅拌1h。在混合液中加入外消旋的2-溴苯丙酸苄酯(243.0mg,1.0mmol)，降低反应液温度至–80℃，逐滴加入2-萘基溴化镁(4.0mL,0.5M THF溶液,2.0mmol)。在–80℃下继续搅拌反应24h，加入饱和氯化铵水溶液淬灭反应。反应液用乙醚（15mL×4）萃取，合并有机层，无水硫酸钠干燥，减压浓缩后经硅胶柱色谱纯化（正己烷/乙酸乙酯30:1），得无色油状物(S)-2-(2-萘 基)丙酸酯3l(214.9mg,产率74%，光学纯度87%)。[α]D 20=+4.7(c1.2,CHCl3);1H NMR(300MHz,CDCl3)δ:7.82–7.72(m,4H),7.47–7.42(m,3H),7.29–7.22(m,5H),5.15(d,J=12.5Hz,1H),5.08(d,J=12.5Hz,1H),3.94(q,J=7.2Hz,1H),1.60(d,J=7.2Hz,3H);13C NMR(75MHz,CDCl3)δ:174.2,137.8,135.9,133.4,132.6,128.4,128.3,128.0,127.9,127.8,127.6,126.13,126.08,125.8,66.5,45.7,18.5;HRMS(ESI)calcd for C20H17O2[M-H]-289.1229,found289.1230。

Claims (10)

1.不对称催化合成(S)-2-芳基丙酸酯新方法，其特征在于：采用不对称催化Kumada交叉偶联的方法，在有机溶剂中，在双噁唑啉/钴催化下，2-卤代丙酸酯与芳基格氏试剂反应合成(S)-2-芳基丙酸酯（式1）。 
Figure FDA0000458375330000011
。
2.根据权利要求1所述的合成方法，其特征在于不对称催化Kumada交叉偶联反应所用的双噁唑啉手性配体的取代基R为苯基、苄基、异丙基、异丁基、叔丁基与苯乙基，优选取代基R为苄基的双噁唑啉手性配体。 
3.根据权利要求1所述的合成方法，其特征在于不对称催化Kumada交叉偶联反应所用的钴盐为CoI2、CoBr2、CoCl2、Co(OAc)2、Co(acac)2、Co(acac)3、Co(dppe)Cl2与Co(PPh3)Cl2：优选CoI2。 
4.根据权利要求1所述的合成方法，其特征在于不对称催化Kumada交叉偶联反应中所用的有机溶剂为四氢呋喃、甲苯、乙醚、二氯甲烷与1,2-二甲氧乙烷，优选四氢呋喃。 
5.根据权利要求1所述的合成方法，其特征在于不对称催化Kumada交叉偶联反应中所用的2-卤代丙酸酯的卤素原子为Cl、Br与I，取代基R为甲基、乙基、异丙基、叔丁基、苯基、苄基、环戊基、环己基、环己甲基、溴乙基与异戊烯基，优选2-溴丙酸苄酯。 
6.根据权利要求1所述的合成方法，其特征在于不对称催化Kumada交叉偶联反应中所用的芳基格氏试剂中的芳基为苯基、萘基、吡啶基、吡咯基、呋喃基，优选苯基格氏试剂。 
7.根据权利要求1所述的合成方法，其特征在于不对称催化Kumada交叉偶联反应中所用的芳基格氏试剂为芳基基溴化镁与芳基氯化镁，优选芳基溴化镁。 
8.根据权利要求1所述的合成方法，其特征在于不对称催化Kumada交叉偶联反应的反应温度为–60℃至–100℃，优选–80℃。 
9.根据权利要求1所述的合成方法，其特征在于不对称催化Kumada交叉偶联反应的中双噁唑啉手性配体与钴盐的摩尔当量比为1:1至1:3，优选1:1.2。 
10.根据权利要求1所述的合成方法，其特征在于不对称催化Kumada交叉偶联反应中卤代羧酸酯与格氏试剂的摩尔当量比为1:1至1:3，优选1:1.4。
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CN105198722A (zh) * 2015-09-24 2015-12-30 中国农业大学 一种不对称催化合成(r)-4,7-二甲基-1-四氢萘酮的方法
CN108026014B (zh) * 2015-09-30 2021-03-16 大正制药株式会社 光学活性的2-(2-氟联苯-4-基)丙酸的制备方法
CN108026014A (zh) * 2015-09-30 2018-05-11 大正制药株式会社 光学活性的2-(2-氟联苯-4-基)丙酸的制备方法
US10207976B2 (en) 2015-09-30 2019-02-19 Taisho Pharmaceutical Co., Ltd Method for producing optically active 2-(2-fluorobiphenyl-4-yl) propanoic acid
CN106748768A (zh) * 2016-11-11 2017-05-31 上海应用技术大学 一种手性α‑芳基丙酸酯类化合物的合成方法
CN106748768B (zh) * 2016-11-11 2019-05-28 上海应用技术大学 一种手性α-芳基丙酸酯类化合物的合成方法
CN109232386A (zh) * 2018-11-12 2019-01-18 中国农业大学 一种不对称合成(s)-丙克拉莫的方法
CN110483289B (zh) * 2019-07-31 2021-02-09 中国农业大学 一种不对称合成手性烯酸酯的方法
CN110483289A (zh) * 2019-07-31 2019-11-22 中国农业大学 一种不对称合成手性烯酸酯的方法
CN111533649A (zh) * 2020-06-01 2020-08-14 南京工业大学 一种酸类化合物的合成方法
CN111533649B (zh) * 2020-06-01 2023-03-21 南京工业大学 一种酸类化合物的合成方法
CN113929577A (zh) * 2021-11-05 2022-01-14 安徽美致诚药业有限公司 一种2-(4-甲基苯基)-丙酸酯的合成方法
CN113929577B (zh) * 2021-11-05 2023-09-29 安徽美致诚药业有限公司 一种2-(4-甲基苯基)-丙酸酯的合成方法

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