CN110903172B - 立体选择性合成(e)-三取代烯烃的方法 - Google Patents

立体选择性合成(e)-三取代烯烃的方法 Download PDF

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CN110903172B
CN110903172B CN201911204164.5A CN201911204164A CN110903172B CN 110903172 B CN110903172 B CN 110903172B CN 201911204164 A CN201911204164 A CN 201911204164A CN 110903172 B CN110903172 B CN 110903172B
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陈建辉
刘红梅
蔡成
丁洋浩
刘波盛
夏远志
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Abstract

本发明属于金属催化合成技术领域，公开了一种立体选择性合成(E)‑三取代烯烃的方法，以1,1‑二取代烯烃为原料，以CoX2和PAO配体的组合为催化剂；在活化试剂的存在下，‑30℃～80℃温度反应0.5分钟～48小时制得(E)‑三取代烯烃；与现有方法相比，本发明的方法所使用的催化剂更为经济、高效、环境友好，同时，反应的官能团容忍性好，反应条件温和，操作简便，无需外加试剂的参与，原子经济性100％。另外，反应无需其他任何的有毒过渡金属(如钌、铑、钯等)盐类的加入，在药物和食品化学工业上具有较大的实际应用价值。

Description

立体选择性合成(E)-三取代烯烃的方法
技术领域
本发明属于金属催化合成技术领域，尤其涉及一种立体选择性合成(E)-三取代烯烃的方法。
背景技术
目前，最接近的现有技术：三取代烯烃广泛存在于天然产物中，同时也是重要的合成子，应用于不对称氢化反应、烯丙化反应以及共轭加成反应中。通过Wittig反应、烯烃复分解和偶联反应等经典方法可以制备三取代烯烃。但是，这些方法合成的三取代烯烃通常E构型和Z构型的混合物，无法得到单一立体构型的三取代烯烃。同一烯烃的E构型和Z构型虽然具有相同的分子构成，相似的物理化学性质，但构型的不同使得它们在某些环境中表现出不同的性质。因此，立体选择性的合成(E)-或(Z)-三取代烯烃是合成化学领域的热点和难点之一[Nature 2017,552,347.]。以1,1-二取代烯烃为原料，使用金属催化烯烃异构化得到三取代烯烃，具有100％的原子经济性，是合成三取代烯烃的较优策略。但这一方法需要解决2个难题：1.效率问题，金属催化剂与1,1-二取代烯烃作用需要克服较大的立体位阻；2.立体选择性控制问题，如何高立体选择性的得到(E)-或(Z)-三取代烯烃。现有三例金属催化1,1-二取代烯烃合成(E)-三取代烯烃的报道；反应方程式如下：
Figure BDA0002296586030000011
综上所述，现有技术存在的问题是：
(1)催化剂昂贵，为钌、铑、钯等贵金属催化剂，有的还需要复杂的配体或者活性金属配合物；
(2)催化效率低，反应时间长(5-29小时)，催化剂的用量大(2-5mol％)；
(3)反应转化率低，立体选择性较差；
(4)底物局限性大，应用的例子少，只适用芳基取代的底物；
解决上述技术问题的难度：如何设计合成合适的配体，发展高效的钴等地球丰产过渡金属催化剂，实现高立体选择性的(E)-三取代烯烃的合成。
解决上述技术问题的意义：三取代烯烃广泛存在于天然产物中，同一烯烃的E构型和Z构型虽然具有相同的分子构成，相似的物理化学性质，但构型的不同使得它们在某些环境中表现出不同的性质。尤其需要注意的是在，药物分子中，构型的不同可能会导致作用效果的差异甚至是相反。三取代烯烃同时也是重要的合成子，应用于不对称氢化反应、烯丙化反应以及共轭加成反应中，E/Z烯烃混合物的原料可能给反应带来区域、立体、非对映体及对映体选择性方面的难题。
发明内容
针对现有技术存在的问题，本发明提供了一种立体选择性合成(E)-三取代烯烃的方法。
本发明是这样实现的，一种立体选择性合成(E)-三取代烯烃的方法，所述立体选择性合成(E)-三取代烯烃的方法以1,1-二取代烯烃为原料，以CoX2和PAO配体的组合为催化剂；在活化试剂的存在下，-30℃～80℃温度反应0.5分钟～48小时制得(E)-三取代烯烃；
所述1,1-二取代烯烃、CoX2、PAO配体、活化试剂的摩尔比为1：0.00001-0.10：0.00001-0.10：0.00003-0.30；
所述1,1-二取代烯烃的结构式为
Figure BDA0002296586030000031
R1，R2任选自取代的芳基、C1-C16的烷基、C1-C16的环烷基、C1-C16的烷氧基、F、Cl、Br、I中的一种；X为F、Cl、Br、I、OAc、CF3SO3中的任意一种。
进一步，所述立体选择性合成(E)-三取代烯烃的方法产物为(E)-三取代烯烃，其结构式为
Figure BDA0002296586030000032
其中R1，R2任选自取代的芳基、C1-C16的烷基、C1-C16的环烷基、C1-C16的烷氧基、F、Cl、Br、I中的一种。
进一步，所述立体选择性合成(E)-三取代烯烃的方法PAO配体为光学纯的如下化合物或其对映体或消旋体，R3和R4任选自氢、C1-C16的烷基、环烷基或芳基中的一种，R5任选自C1-C16的烷基、环烷基或芳基中的一种。
进一步，所述立体选择性合成(E)-三取代烯烃的方法催化剂为CoXn-PAO络合物，为光学纯的如下络合物或其对映体或消旋体；其中，R3、R4任选自氢、C1-C16的烷基、环烷基或芳基，R5任选自C1-C16的烷基、环烷基或芳基；X选自H、烷基，芳基、卤素、拟卤化物、羧酸、磺酸、膦酸的阴离子中的任意一种；n1为X的个数，为1、2、3；n2为PAO配体二苯胺上氢的个数，为0或1；
卤素为F、Cl、Br、I；拟卤化物为氰化物、氰酸、盐、异氰酸盐；膦酸的阴离子为碳酸根、甲酸根、乙酸根、丙酸根、甲基磺酸根、三氯甲基磺酸根、苯基磺酸根、甲苯磺酸根。
进一步，所述立体选择性合成(E)-三取代烯烃的方法活化试剂任选自三乙基硼氢化钠、三乙基硼氢化锂、三异丁基硼氢化钠、叔丁醇钠、叔丁醇钾、硅烷、硼烷中的任意一种。
进一步，所述立体选择性合成(E)-三取代烯烃的方法有机溶剂是二氧六环、四氢呋喃、乙醚、甲苯、二氯甲烷、正己烷、苯、四氯化碳、乙腈、石油醚、环己烷、乙酸乙酯、三氯甲烷、N,N-二甲酰胺中的任意一种。
进一步，所述立体选择性合成(E)-三取代烯烃的方法溶剂为二氧六环。
本发明的另一目的在于提供一种由所述立体选择性合成(E)-三取代烯烃的方法合成的(E)-三取代烯烃。
综上所述，本发明的优点及积极效果为：本发明使用廉价的钴催化剂，以简单易得的1,1-二取代烯烃为原料，经由双键异构化反应高效地立体选择性合成(E)-三取代烯烃。本发明使用的催化剂和原料廉价易得，操作简便，反应过程无需其他外加试剂的参与，原子经济性100％，具有非常高的工业化应用前景。本发明提供一种有效的立体选择性地合成(E)-三取代烯烃的方法，是以钴金属盐和PAO配体的组合为催化剂，催化1,1-二取代烯烃发生双键异构化转化，高效率、高立体选择性的得到相应的(E)-烯烃。
钴催化1,1-二取代烯烃发生双键异构化，通过溶剂效应调控，高效地合成相应(E)-三取代烯烃的方法。与现有方法相比，本发明的方法所使用的原料更为廉价易得，官能团容忍性好，反应条件温和，操作简便，反应过程无需外加试剂的参与，原子经济性100％。另外，反应无需其他任何的有毒过渡金属(如钌、铑、钯等)盐类的加入，在药物和食品化学工业上具有较大的实际应用价值。
附图说明
图1是本发明实施例提供的立体选择性合成(E)-三取代烯烃的方法流程图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
针对现有技术存在的问题，本发明提供了一种立体选择性合成(E)-三取代烯烃的方法，下面结合附图对本发明作详细的描述。
如图1所示，本发明实施例提供的立体选择性合成(E)-三取代烯烃的方法包括以下步骤：
S101：以CoX2和PAO配体的组合为催化剂；
S102：在活化试剂的存在下，-30℃～80℃温度反应0.5分钟～48小时制得(E)-或(Z)-三取代烯烃。
本发明是以1,1-二取代烯烃为原料，在三乙基硼氢化钠存在下，在有机溶剂中，以CoX2和PAO配体的组合或CoX2-PAO络合物尤其作为催化剂反应进行的，立体选择性地得到(E)-三取代烯烃，可用下式表示：
Figure BDA0002296586030000051
1,1-二取代烯烃的结构式为
Figure BDA0002296586030000052
其中，R1和R2如前所述；PAO配体和CoX2-PAO的结构通式分别如下所示(为任意光学纯的结构、或其对映体或消旋体，不受图示所限)
Figure BDA0002296586030000053
R3、R4任选自氢、C1-C16的烷基、环烷基或芳基，R5任选自C1-C16的烷基、环烷基或芳基；X选自H、烷基，芳基、卤素(F、Cl、Br、I)、拟卤化物(氰化物、氰酸、盐、异氰酸盐)、羧酸、磺酸、膦酸的阴离子(碳酸根、甲酸根、乙酸根、丙酸根、甲基磺酸根、三氯甲基磺酸根、苯基磺酸根、甲苯磺酸根)中的任意一种；n为X的个数，为1、2、3。
所述的1,1-二取代烯烃、CoX2、PAO配体、三乙基硼氢化钠的摩尔比为1：0.00001-0.10：0.00001-0.10：0.00003-0.30，进一步1：0.005-0.05：0.005-0.05：0.015-0.15，尤其推荐(Z)-烯烃、CoX2、PAO配体、三乙基硼氢化钠的摩尔比为1：0.001：0.001：0.003。
反应温度推荐为-30℃～80℃，进一步推荐0℃～60℃，尤其推荐25℃。
反应时间推荐为0.5分钟-48小时，进一步推荐1分钟-3小时，尤其推荐10分钟。
本发明中提到的烷基，均推荐碳数为1～16的基团，进一步推荐碳数为1～10，尤其推荐碳数为1～6的。本发明提到的环烷基，均推荐碳数为3～16的基团，进一步推荐碳数为3～10，尤其推荐碳数为3～6的。本发明提到的芳基，均指苯基、萘基和含N，O，S的杂芳基。
本发明方法的反应可以在无溶剂下进行，也可以在在极性或非极性溶剂中进行，如二氧六环、四氢呋喃、乙醚、甲苯、二氯甲烷、正己烷、苯、四氯化碳、乙腈、石油醚、环己烷、乙酸乙酯、三氯甲烷、N,N-二甲酰胺中等。
本发明方法可以通过重结晶、薄层层析、柱层析或减压蒸馏加以分离得到产物。
下面通过具体实施例对本发明的技术方案作进一步的描述。
实施例1：催化异构化合成E-三取代烯烃
Figure BDA0002296586030000061
反应操作：25℃下，在一干燥的反应试管中加入CoCl2(0.01mmol)，PAO配体(0.01mmol)，烯烃(10mmol)，甲苯(1mL)，注射入三乙基硼氢化钠(0.03mmol)，然后在室温下搅拌10分钟后柱层析分离得到产物。
产物1：(E)-1-(But-2-en-2-yl)-4-methoxybenzene
Figure BDA0002296586030000062
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.33-7.28(m,2H),6.87-6.82(m,2H),5.83-5.73(m,1H),3.80(s,3H),2.03-1.98(m,3H),1.78(dq,J＝6.8,1.2Hz,3H).
产物2：(E)-1-(But-2-en-2-yl)-3-methoxybenzene.
Figure BDA0002296586030000071
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.22(t,J＝7.8Hz,1H),6.97(d,J＝7.8Hz,1H),6.93-6.89(m,1H),6.79-6.74(m,1H),5.91-5.83(m,1H),3.81(s,3H),2.01(s,3H),1.79(dq,J＝6.8,1.0Hz,3H).13C NMR:(100.6MHz,CDCl3)delta 159.4,145.6,135.4,129.0,122.6,118.1,111.6,111.4,55.1,15.5,14.2.
产物3：(E)-but-2-en-2-ylbenzene
Figure BDA0002296586030000072
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.39-7.34(m,2H),7.33-7.27(m,2H),7.23-7.18(m,1H),5.86(q,J＝6.8Hz,1H),2.05-2.00(m,3H),1.80(dq,J＝6.8,1.2Hz,3H).
产物4：(E)-1-(But-2-en-2-yl)-4-methylbenzene
Figure BDA0002296586030000073
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.27(d,J＝8.2Hz,2H),7.11(d,J＝7.8Hz,2H),5.83(q,J＝6.8Hz,1H),2.33(s,3H),2.03-1.99(m,3H),1.78(dq,J＝6.8,1.0Hz,3H).
产物5：(E)-1-(But-2-en-2-yl)-4-ethylbenzene
Figure BDA0002296586030000074
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.29(d,J＝8.4Hz,2H),7.14(d,J＝8.4Hz,2H),5.83(q,J＝7.0Hz,1H),2.63(q,J＝7.6Hz,2H),2.04-2.00(m,3H),1.78(dq,J＝7.0Hz,3H),1.23(t,J＝7.6Hz,3H).13C NMR:(100.6MHz,CDCl3)delta 142.4,141.4,135.3,127.6,125.4,121.6,77.3,77.0,76.7,28.4,15.6,15.4,14.3.
产物6：(E)-4-(But-2-en-2-yl)-1,1'-biphenyl
Figure BDA0002296586030000081
白色固体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.63-7.57(m,2H),7.57-7.52(m,2H),7.47-7.39(m,4H),7.36-7.30(m,1H),5.94(q,J＝7.0Hz,1H),2.06(s,3H),1.82(d,J＝7.0Hz,3H).13C NMR:(100.6MHz,CDCl3)delta 142.9,140.9,139.2,135.0,128.7,127.1,126.9,126.8,125.8,122.6,15.4,14.4.HRMS:(ESI)calculated for[C16H16]:209.1325[M+H]+,found209.1318.
产物7：(E)-4-(But-2-en-2-yl)-N,N-dimethylaniline
Figure BDA0002296586030000082
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.30-7.26(m,2H),6.72-6.67(m,2H),5.75(qq,J＝6.8,1.2Hz,1H),2.93(s,6H),2.01-1.98(m,3H),1.77(dq,J＝6.8,1.2Hz,3H).13C NMR:(125.8MHz,CDCl3)delta 149.4,135.0,132.5,126.1,119.1,112.5,40.6,15.3,14.2.
产物8：(E)-(4-(But-2-en-2-yl)phenoxy)(tert-butyl)dimethylsilane
Figure BDA0002296586030000083
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.25-7.20(m,2H),6.80-6.74(m,2H),5.78(q,J＝6.8Hz,1H),1.99(s,3H),1.77(d,J＝6.8Hz,3H),0.98(s,9H),0.19(s,6H).13C NMR:(100.6MHz,CDCl3)delta 154.3,137.1,134.9,126.3,120.8,119.6,18.2,15.4,14.2,-4.4.HRMS:(ESI)calculated for[C16H26OSi]:263.1826[M+H]+,found 263.1825.
产物9：(E)-(4-(But-2-en-2-yl)phenyl)(methyl)sulfane
Figure BDA0002296586030000084
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.32-7.27(m,2H),7.23-7.18(m,2H),5.85(q,J＝6.8Hz,1H),2.47(s,3H),2.00(s,3H),1.79(d,J＝6.8Hz,3H).13C NMR:(100.6MHz,CDCl3)delta 140.9,136.0,134.7,126.6,125.8,122.0,77.3,77.0,76.7,16.0,15.2,14.3.HRMS:(ESI)calculated for[C11H14S]:179.0889[M+H]+,found 179.0883.
产物10：(E)-4-(But-2-en-2-yl)phenyl acetate
Figure BDA0002296586030000091
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.40-7.32(m,2H),7.28-7.23(m,2H),5.89-5.78(m,1H),2.29(s,3H),2.01(s,3H),1.83-1.75(m,3H).13CNMR:(100.6MHz,CDCl3)delta 169.5,149.1,141.7,134.6,126.4,122.6,121.0,21.0,15.4,14.2.HRMS:(ESI)calculated for[C12H14O2]:191.1067[M+H]+,found 191.1060.
产物11：(E)-2-(but-2-en-2-yl)-6-methoxynaphthalene
Figure BDA0002296586030000092
白色固体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.73-7.69(m,2H),7.68-7.64(m,1H),7.57-7.52(m,1H),7.15-7.08(m,2H),5.99(q,J＝6.8Hz,1H),3.91(s,3H),2.14-2.10(m,3H),1.85(dq,J＝6.8,1.0Hz,3H).13C NMR:(100.6MHz,CDCl3)delta157.3,139.0,135.2,133.3,129.5,128.9,126.4,124.7,123.6,122.2,118.7,105.5,55.2,15.4,14.4.HRMS:(ESI)calculated for[C15H16O]:213.1274[M+H]+,found 213.1292.
产物12：(E)-1-(But-2-en-2-yl)-4-fluorobenzene
Figure BDA0002296586030000093
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.34-7.28(m,2H),7.01-6.94(m,2H),5.79(q,J＝6.8Hz,1H),2.02-1.98(m,3H),1.78(dq,J＝6.8,1.0Hz,3H).13C NMR:(100.6MHz,CDCl3)delta 161.7(d,J＝304.1),140.1,134.5,126.9(d,J＝9.4),122.3,114.8(d,J＝26.6),15.6,14.3.19F NMR:(470MHz,CDCl3)δ-117.0.
产物13：(E)-1-(But-2-en-2-yl)-2-fluorobenzene
Figure BDA0002296586030000094
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.23-7.14(m,2H),7.10-6.95(m,2H),5.67(q,J＝7.0Hz,1H),2.03-1.98(m,3H),1.78(dq,J＝7.0,1.0Hz,3H).13C NMR:(100.6MHz,CDCl3)delta 159.9(d,J＝244.8),132.9(d,J＝14.5),132.1,129.7(d,J＝4.5),127.9(d,J＝8.1),125.7(d,J＝1.75),123.8(d,J＝3.6),115.6(d,J＝22.5),16.6,14.0.19F NMR:(470MHz,CDCl3)δ-115.7.
产物14：(E)-1-(But-2-en-2-yl)-4-(trifluoromethyl)benzene
Figure BDA0002296586030000101
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.54(d,J＝8.2Hz,2H),7.45(d,J＝8.2Hz,2H),5.94(q,J＝7.0Hz,1H),2.06-2.00(m,3H),1.82(dq,J＝7.0,1.0Hz,3H).13C NMR:(125.8MHz,CDCl3)delta 147.6,134.6,128.5(q,J＝31.6),125.8,125.1(q,J＝3.6),124.7,124.4(q,J＝270.0),15.3,14.3.19F NMR:(470MHz,CDCl3)δ-115.7.
产物15：(E)-4-(4-fluorophenyl)pent-3-enoate.
Figure BDA0002296586030000102
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.35-7.28(m,2H),7.02-6.94(m,2H),5.67(t,J＝7.2Hz,1H),4.14(q,J＝7.2Hz,2H),2.56-2.40(m,4H),2.03(s,3H),1.26(t,J＝7.2Hz,3H).13C NMR:(125.8MHz,CDCl3)delta 173.1,161.8(d,J＝304.8),139.6(d,J＝4.0),135.1,127.1(d,J＝10.1),125.9,114.8(d,J＝26.6),60.3,34.1,24.2,15.9,14.2.19F NMR:(470MHz,CDCl3)δ-116.4.HRMS:(ESI)calculated for[C14H17FO2]:237.1285[M+H]+,found237.1288.
产物16：(E)-1-(But-2-en-2-yl)-4-chlorobenzene
Figure BDA0002296586030000103
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.31-7.23(m,4H),5.85(q,J＝6.8Hz,1H),2.00(s,3H),1.79(d,J＝6.8Hz,3H).
产物17：(E)-1-(but-2-en-2-yl)-3-chlorobenzene
Figure BDA0002296586030000104
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.36-7.32(m,1H),7.24-7.15(m,3H),5.88(q,J＝6.8Hz,1H),2.00(s,3H),1.80(dq,J＝6.8,1.0Hz,3H).13C NMR:(100.6MHz,CDCl3)delta 145.8,134.4,134.0,129.3,126.3,125.7,123.7,123.6,15.3,14.3.
产物18：(E)-1-Bromo-4-(but-2-en-2-yl)benzene
Figure BDA0002296586030000105
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.44-7.37(m,2H),7.27-7.19(m,2H),5.85(q,J＝7.0Hz,1H),1.99(s,3H),1.78(d,J＝7.0Hz,3H).
产物19：(E)-Pent-2-en-2-ylbenzene
Figure BDA0002296586030000111
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.41-7.35(m,2H),7.33-7.26(m,2H),7.23-7.16(m,1H),5.77(tq,J＝7.2,1.4Hz,1H),2.21(quint,J＝7.6Hz,2H),2.05-2.00(m,3H),1.06(t,J＝7.6Hz,3H).
产物20：(E)-Hex-2-en-2-ylbenzene
Figure BDA0002296586030000112
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.41-7.35(m,2H),7.33-7.26(m,2H),7.23-7.17(m,1H),5.79(tq,J＝7.2,1.2Hz,1H),2.18(q,J＝7.2Hz,2H),2.03(s,3H),1.48(sext,J＝7.4Hz,2H),0.96(t,J＝7.4Hz,3H).
产物21：(E)-hept-2-en-2-ylbenzene
Figure BDA0002296586030000113
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.41-7.35(m,2H),7.30(t,J＝7.2Hz,2H),7.21(t,J＝7.2Hz,1H),5.78(tq,J＝7.4,1.4Hz,1H),2.20(q,J＝7.4Hz,2H),2.03(s,3H),1.49-1.30(m,4H),0.93(t,J＝7.2Hz,3H).
产物22：(E)-5-(Pent-2-en-2-yl)benzo[d][1,3]dioxole
Figure BDA0002296586030000114
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ6.91-6.88(m,1H),6.87-6.82(m,1H),6.77-6.72](m,1H),5.93(s,2H),5.67(tq,J＝7.2,1.2Hz,2H),2.18(quint,J＝7.6Hz,2H),2.00-1.96(m,3H),1.04(t,J＝7.6Hz,3H).13C NMR:(100.6MHz,CDCl3)delta147.5,146.1,138.4,133.5,129.2,118.8,107.8,106.2,100.8,21.9,15.8,14.0.HRMS:(ESI)calculated for[C12H14O2]:191.1067[M+H]+,found 191.1070.
产物23：(E)-2-(But-2-en-2-yl)thiophene
Figure BDA0002296586030000115
无色油状液体，产率>99％，E/Z>99/1。1H NMR:(400.0MHz,CDCl3)δ7.10-7.05(m,1H),6.97-6.90(m,2H),6.01(q,J＝7.0Hz,1H),2.03(s,3H),1.78(d,J＝7.0Hz,3H).13CNMR:(125.8MHz,CDCl3)delta 148.1,129.7,127.1,122.6,121.7,121.5,76.7,15.4,13.9.
实施例2：三取代烯烃的不对称环氧化反应对比
Figure BDA0002296586030000121
反应操作：室温下，在一干燥的反应试管中加入Salen-Mn催化剂(0.05mmol)，烯烃(1mmol)，二氯甲烷(DCM)(2mL)，次氯酸钠(NaOCl)(1.5mmol)，然后在0℃下搅拌3小时后柱层析分离得到产物。
以E/Z-三取代烯烃混合物(E/Z＝20/80)为原料的反应得到环氧化反应混合产物，比例为1：4。以E-三取代烯烃(E/Z>99/1)为原料的反应得到产物24。
产物24：(2S,3S)-2,3-dimethyl-2-phenyloxirane
Figure BDA0002296586030000122
无色油状液体，产率82％，93％ee。1HNMR:(400.0MHz,CDCl3)δ7.20-7.37(m,5H),2.97(q,J＝5.6Hz,1H),1.69(s,3H),1.45(d,J＝5.4Hz,3H)；13C NMR(100MHz,CDCl3)δ:143.5,128.7,127.6,125.4,62.9,60.6,17.8,14.9.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (4)

1.一种立体选择性合成(E)-三取代烯烃的方法，其特征在于，所述立体选择性合成(E)-三取代烯烃的方法以1,1-二取代烯烃为原料，以CoX2和PAO配体的组合为催化剂；在活化试剂的存在下，-30℃～80℃温度反应0.5分钟～48小时制得(E)-三取代烯烃；
所述1,1-二取代烯烃、CoX2、PAO配体、活化试剂的摩尔比为1：0.00001-0.10：0.00001-0.10：0.00003-0.30；
所述PAO配体为光学纯的化合物
Figure FDA0003152220500000011
或其对映体或消旋体，R3和R4任选自氢、C1-C16的烷基、环烷基或芳基中的一种，R5任选自C1-C16的烷基、环烷基或芳基中的一种；
所述1,1-二取代烯烃的结构式为
Figure FDA0003152220500000012
R1，R2任选自取代的芳基、C1-C16的烷基、C1-C16的环烷基、C1-C16的烷氧基、F、Cl、Br、I中的一种；X为F、Cl、Br、I、OAc、CF3SO3中的任意一种；
所述活化试剂任选自三乙基硼氢化钠、三乙基硼氢化锂、三异丁基硼氢化钠、叔丁醇钠、叔丁醇钾、硅烷、硼烷中的任意一种。
2.如权利要求1所述的立体选择性合成(E)-三取代烯烃的方法，其特征在于，所述立体选择性合成(E)-三取代烯烃的方法产物为(E)-三取代烯烃，其结构式为
Figure FDA0003152220500000013
其中R1，R2任选自取代的芳基、C1-C16的烷基、C1-C16的环烷基、C1-C16的烷氧基、F、Cl、Br、I中的一种。
3.如权利要求1所述的立体选择性合成(E)-三取代烯烃的方法，其特征在于，所述立体选择性合成(E)-三取代烯烃的方法催化剂为CoXn-PAO络合物，光学纯的络合物
Figure FDA0003152220500000021
或其对映体或消旋体；其中，R3、R4任选自氢、C1-C16的烷基、环烷基或芳基，R5任选自C1-C16的烷基、环烷基或芳基；X为F、Cl、Br、I、OAc、CF3SO3中的任意一种；n为X的个数，为1、2、3。
4.如权利要求1所述的立体选择性合成(E)-三取代烯烃的方法，其特征在于，所述立体选择性合成(E)-三取代烯烃的方法有机溶剂是二氧六环、四氢呋喃、乙醚、甲苯、二氯甲烷、正己烷、苯、四氯化碳、乙腈、石油醚、环己烷、乙酸乙酯、三氯甲烷、N,N-二甲酰胺中的任意一种。
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