CN109225334A - 一种具有邻位空间位阻结构的钌烯烃复分解催化剂及其制备方法和应用 - Google Patents
一种具有邻位空间位阻结构的钌烯烃复分解催化剂及其制备方法和应用 Download PDFInfo
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- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
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Abstract
本发明公开了一种具有邻位空间位阻结构的钌烯烃复分解催化剂及其制备方法和应用。该催化剂具有如下结构通式且包括以下制备方法：(1)将Zn(OAc)2·2H2O和化合物(I)溶于异丙醇溶剂中，再加入乙二胺，反应后过滤沉淀的固体，用甲醇和氯仿洗涤，真空干燥得化合物(Ⅱ)；(2)在氮气条件下，将Grubbs‑Hoveyda II和化合物(Ⅱ)加入到干燥的四氢呋喃溶剂中，反应后在N2下将溶剂离心，收集溶液后，将其排干至固体，用无水乙醚洗涤，干燥得本发明钌烯烃复分解催化剂化合物(Ⅲ)。本发明方法的步骤简单，反应条件温和，在室温下反应，能得到具有特定构型的顺式结构产物，具有广泛的应用前景。
Description
技术领域
本发明涉及一种具有邻位空间位阻结构的钌烯烃复分解催化剂及其制备方法和应用，属于过渡金属有机催化剂领域。
背景技术
烯烃复分解反应是简单、快捷、高效的合成过程，人们已成功的将烯烃复分解反应用于合成复杂有机分子，功能性高分子等领域。目前，在烯烃复分解领域已经取得了突出的研究成果，同时在这一领域仍然面临不少挑战性的难题。2009年，Schrock和Hoveyda合成了一种含单吡咯配体钼芳氧基配合物，发现其在开环/交叉复分解反应中可以给出高比例的Z式烯烃产物。但是，此类催化剂的官能团兼容性较差，某些常见的有机官能团会使催化剂失活，严重制约此类催化剂在有机合成中广泛应用(I.I.brahem,M.Yu,R.R.Schrock,A.H.Hoveyda,J.Am.Chem.Soc.,2009,131,3844.)。2011年，Grubbs课题组首次报到了含有一种N-杂环卡宾配合物的钌卡宾烯烃复分解催化剂，可以高效的催化末端烯烃交叉复分解反应，并且具有优良的Z-选择性(K.Endo,R.H.Grubbs,J.Am.Chem.Soc.,2011,133(22),8525.)。2013年，Hoveyda课题组发现1,2-苯二硫酚为配体取代的钌配合物可催化张力环的开环移位复分解反应，并具有一定的Z-选择性(R.K.M.Khan,S.Torker,A.H.Hoveyda,J.Am.Chem.Soc.,2014,136,14337.)。之后的进一步研究发现，如果苯二硫酚配体带有卤素取代基，会明显提高催化剂的稳定性以及催化活性，转化率以及Z-选择性都较高(M.J.Koh,R.K.M.Khan,S.Torker,M.Yu,M.S.Mikus,A.H.Hoveyda,Nature,2015,517,181.)。
综上所述，钌卡宾催化剂是具有较好应用前景的烯烃复分解催化剂，尤其是含有双硫螯合配体类的钌卡宾催化剂，因此类催化剂合成路线简单，官能团适用性强，应用前景广阔。但这类催化剂的设计，到目前为止仅考虑了配体的电子效应。如果在催化剂的设计方面，再考虑空间阻碍的作用，则可产生一类性能更加优越的烯烃复分解催化剂。
发明内容
有鉴于此，本发明提供了一种具有邻位空间位阻结构的钌烯烃复分解催化剂及其制备方法和应用，本发明为了解决现有技术的不足，以稳定性、官能团相容性较好的Hoveyda-GrubbsII型配合物为起始原料，Hoveyda-GrubbsII为第二代Hoveyda-Grubbs催化剂，与所合成的具有邻位大空阻的2-巯基苯酚配体反应制备含硫、氧螯合配位的钌卡宾配合物。
为了实现上述目的，本发明采用如下技术方案：
一种具有邻位空间位阻结构的钌烯烃复分解催化剂，其特征在于，所述催化剂具有如下结构通式：
其中：通式中的R为甲基、异丙基、叔丁基中的任一种。
本发明的有益效果为：此类催化剂结构通式中含有一个邻位具有大位阻的硫、氧螯合配体与钌金属中心相结合。在这一构型中，由于空间阻碍、电子效应的协同作用，使得酚氧占据与氮杂环卡宾配体对位的位置。
相比硫原子，氧的亲核性较弱，且邻位有大基团取代，因此，这种配位模式可有效避免双硫配位的钌卡宾配合物中位于氮杂环卡宾配体对位的硫配体对卡宾碳进行亲核加成反应而产生的严重分解。
该催化剂可使催化剂的适用范围进一步拓展到空阻较大、缺电子的烯烃底物；由于所设计的硫氧螯合配体具有大空间阻碍取代基，可增加硫酚配体与氮杂环卡宾配体之间的排斥力，从而迫使配体尽量远离同样拥有大空阻的氮杂环卡宾配体，使催化剂拥有接近中间过渡态的三角双锥型配位结构，从而提高催化剂的催化活性。
由于所设计的硫氧螯合配体具有较大的空间阻碍作用，因而可以使催化剂在反应过程中产生的过渡态具有更为紧凑的空间环境，提高四元环过渡态中的对取代基团的立体控制能力。
本发明还提供了制备上述具有邻位空间位阻结构的钌烯烃复分解催化剂的制备方法，该方法包括下列步骤：
(1)将Zn(OAc)2·2H2O和化合物(I)按摩尔比为1:(0.2-0.4)溶于异丙醇溶剂中，所述异丙醇的加入量为每1mmol化合物(I)对应加入异丙醇2-3ml，再加入乙二胺，所述乙二胺的加入量为每1mmol化合物(I)对应加入乙二胺0.3-0.4g，将所得混合物在18℃-25℃下搅拌0.5-3小时。过滤沉淀的固体，用甲醇和氯仿洗涤3次，甲醇和氯仿的体积比为1:(1-2)，真空干燥，得到化合物(Ⅱ)；
(2)在氮气条件下，将Grubbs-Hoveyda II和化合物(Ⅱ)按摩尔比为1:(1-2)加入到干燥的四氢呋喃溶剂中，所述四氢呋喃的加入量为：每1mmol化合物(Ⅱ)对应加入四氢呋喃7-9ml，将所得混合物在4℃-10℃下搅拌1-3小时，然后在N2下将溶剂离心。收集溶液后，将其排干至固体，用无水乙醚洗涤3次，干燥得化合物(Ⅲ)；
化合物(I)的化学式为化合物(Ⅱ)的化学式为化合物(Ⅲ)的化学式为
其中：R均为甲基、异丙基、叔丁基中的任一种。
本发明的有益效果为：
本发明方法的步骤简单，反应条件温和，在室温下反应，能得到具有特定构型的顺式结构产物。
具体实施方式
以下的实施例在于详细说明本发明，只是本发明的较佳实施例，并非限制本发明。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
以下所述化合物(Ⅱ-1)、(Ⅱ-2)、(Ⅱ-3)分别表示取代基为甲基、异丙基、叔丁基的化合物(Ⅱ)；(Ⅲ-1)、(Ⅲ-2)、(Ⅲ-3)分别表示取代基为甲基、异丙基、叔丁基的化合物(Ⅲ)。
实施例1
2-巯基-6-甲基苯酚锌的合成
将Zn(OAc)2·2H2O(6.1357g，27.95mmol)和2-巯基-6-甲基苯酚(1.1859g，8.47mmol)溶于i-PrOH(20mL)中。将乙二胺(3.05g，50.82mmol)加入到该溶液中，并将所得混合物在22℃下搅拌1小时。过滤沉淀的固体，用甲醇(10.0mL)和氯仿(10.0mL)洗涤后，将固体真空干燥，得到白色固体2-巯基-6-甲基苯酚锌(Ⅱ-1)(1.1524g，5.67mmol，67％收率)。
实施例2
2-巯基-6-异丙基苯酚锌的合成
将Zn(OAc)2·2H2O(6.1357g，27.95mmol)和2-巯基-6-异丙基苯酚(1.4231g，8.47mmol)溶于i-PrOH(20mL)中。将乙二胺(3.05g，50.82mmol)加入到该溶液中，并将所得混合物在22℃下搅拌1小时。过滤沉淀的固体，用甲醇(10.0mL)和氯仿(10.0mL)洗涤后，将固体真空干燥，得到白色固体2-巯基-6-异丙基苯酚锌(Ⅱ-2)(1.1351g，4.91mmol，58％收率)。
实施例3
2-巯基-6-叔丁基苯酚锌的合成
将Zn(OAc)2·2H2O(6.1357g，27.95mmol)和2-巯基-6-叔丁基苯酚(1.5416g，8.47mmol)溶于i-PrOH(20mL)中。将乙二胺(3.05g，50.82mmol)加入到该溶液中，并将所得混合物在22℃下搅拌1小时。过滤沉淀的固体，用甲醇(10.0mL)和氯仿(10.0mL)洗涤后，将固体真空干燥，得到白色固体2-巯基-6-叔丁基苯酚锌(Ⅱ-3)(0.9546g，3.89mmol，46％收率)。
实施例4
钌配合物(Ⅲ-1)的合成
在N2气氛下，将Grubbs-Hoveyda II(250mg，0.40mmol)和(Ⅱ-1)(120mg，0.59mmol)加入到有搅拌的反应瓶中，在0℃加入5mL THF。将得到的混合物在6℃下搅拌1小时，然后在N2下将溶剂离心。收集溶液后，将其排干至固体，并将固体用无水乙醚(3×5mL)洗涤并干燥。该产品纯度足够，不需要进一步纯化。得到橙褐色固体Ru-基络合物(Ⅲ-1)(216mg，0.31mmol，产率78％)。
经检测，钌配合物(Ⅲ-1)1H NMR(400MHz,CDCl3)：δ15.61(s,1H),7.31(t,J＝6.6Hz,1H),7.20(d,J＝6.8Hz,1H),7.11(d,J＝7.6Hz,1H),7.02(s,2H),6.87(d,J＝6.6Hz,1H),6.59(s,3H),6.45(d,J＝6.8Hz,2H),5.23-5.08(m,1H),3.87(s,4H),2.45(s,6H),2.30(s,9H),2.06(s,3H),1.61(d,J＝4.7Hz,3H),1.29(s,3H),1.23(d,J＝4.0Hz,3H)ppm.13CNMR(100MHz,CDCl3)：δ165.15,154.98,143.30,136.81,134.46,129.93,129.27,126.72,124.93,123.43,123.12,122.79,116.48,115.85,80.56,23.51,21.06,20.83,17.16ppm.IR(KBr):3265.32,3147.25,2919.04,2733.12,1683.54,1579.64,1480.09,1450.53,1410.92,1261.70,1181.84,1109.73,1065.07,1032.41,954.52,913.69,875.45,847.93,746.58,661.37,574.22,498.57,445.42cm-1.ESI-MS[M+H]+calcd for C38H44N2O2RuS:694.2167；found:695.2274。
实施例5
钌配合物(Ⅲ-2)的合成
在N2气氛下，将Grubbs-Hoveyda II(250mg，0.40mmol)和Ⅱ-2(120mg，0.52mmol)加入到有搅拌的反应瓶中，在0℃加入5mL THF。将得到的混合物在6℃下搅拌1小时，然后在N2下将溶剂离心。收集溶液后，将其排干至固体，并将固体用无水乙醚(3×5mL)洗涤并干燥。得到橙褐色固体Ru-基配合物(Ⅲ-2)(205mg，0.28mmol，产率71％)。
经检测，钌配合物(Ⅲ-2)1H NMR(400MHz,CDCl3):δ15.57(s,1H),7.30(t,J＝7.5Hz,1H),7.20(d,J＝7.3Hz,1H),7.11(d,J＝8.1Hz,1H),7.02(s,2H),6.86(t,J＝7.1Hz,1H),6.65(d,J＝7.1Hz,2H),6.59(d,J＝7.3Hz,1H),6.52(t,J＝7.3Hz,1H),6.38(s,1H),5.20-5.03(m,1H),3.88(s,4H),3.33-3.16(m,1H),2.46(s,6H),2.27(s,9H),1.64(d,J＝6.2Hz,3H),1.30-1.17(m,6H),1.07-0.99(m,6H)ppm.13C NMR(100MHz,CDCl3):δ163.77,154.88,143.25,134.53,134.13,129.24,126.62,124.72,123.42,123.16,117.58,116.54,116.15,80.77,26.87,23.78,23.22,21.80,21.03ppm.IR(KBr):3259.98,3149.89,2956.12,2918.03,1684.57,1579.00,1479.30,1417.34,1325.77,1263.93,1222.36,1186.13,1102.30,1029.73,915.79,842.97,804.22,742.92,665.33,574.57,467.32cm- 1.ESI-MS[M+H]+calcd for C40H48N2O2RuS:722.2480；found:723.2592。
实施例6
钌配合物(Ⅲ-3)的合成
在N2气氛下，将Grubbs-Hoveyda II(250mg，0.40mmol)和(Ⅱ-3)(120mg，0.49mmol)加入到有搅拌的反应瓶中，在0℃加入5mL THF。将得到的混合物在6℃下搅拌1小时，然后在N2下将溶剂离心。收集溶液后，将其排干至固体，并将固体用无水乙醚(3×5mL)洗涤并干燥。得到橙褐色固体Ru-基络合物(Ⅲ-3)(244mg，0.33mmol，产率83％)。
经检测，钌配合物(Ⅲ-3)1H NMR(600MHz,CDCl3):δ15.63(s,1H),7.29(t,J＝7.2Hz,1H),7.24-7.19(m,1H),7.06(d,J＝8.2Hz,1H),7.03-6.95(m,2H),6.84(t,J＝7.3Hz,1H),6.72(d,J＝7.4Hz,2H),6.63-6.56(m,1H),6.47(t,J＝7.5Hz,1H),6.30(s,1H),5.18(dt,J＝13.2,6.6Hz,1H),3.49(q,J＝7.0Hz,4H),2.47(s,6H),2.34-2.17(m,9H),1.68(d,J＝6.6Hz,3H),1.34(d,J＝10.1Hz,3H),1.26(d,J＝6.5Hz,3H),1.23(d,J＝3.7Hz,9H)ppm.13C NMR(150MHz,CDCl3):δ164.94,154.69,142.63,135.73,130.43,129.58,129.32,129.06,126.56,125.59,123.22,122.78,118.86,115.97,115.72,79.56,65.88,34.46,29.88,23.93,21.68,21.01,15.32ppm.IR(KBr):3249.06,3144.86,2952.62,2917.37,2733.83,1684.83,1577.97,1479.67,1450.68,1409.09,1262.58,1107.17,1029.93,927.96,848.83,807.29,744.37,652.67,575.18,521.54,479.39,420.63cm-1.ESI-MS[M+H]+calcd for C41H50N2O2RuS:736.2636；found:737.2634。
实施例7
(E)-5-(4-硝基苯氧基)戊-2-烯-1-醇
在N2气氛下，在带有搅拌的干燥10mL反应瓶中加入1-(丁-3-烯-1-氧基)-4-硝基苯(0.15mmol)和Z-2-丁烯-1,4-二醇(0.30mmol)。向混合物中加入Ru-配合物Ⅲ-20.31mol，四氢呋喃0.5mL，然后在20℃-30℃下剧烈搅拌6小时直到反应结束。真空除去有机溶剂，然后通过硅胶柱色谱纯化残余物得到预期产物。
(E)-5-(4-硝基苯氧基)戊-2-烯-1-醇：淡黄色油状液体，产率93％。
1H NMR(400MHz,CDCl3)：δ8.19(d,J＝9.1Hz,2H),6.93(d,J＝9.2Hz,2H),5.91-5.69(m,2H),4.14(d,J＝3.2Hz,2H),4.09(t,J＝6.5Hz,2H),2.58(dd,J＝11.5,5.8Hz,2H),1.52(s,1H).13C NMR(100MHz,CDCl3)：δ163.92,141.49,132.20,127.27,125.94,114.45,68.05,63.38,31.85ppm。
以下实施例的催化反应与实施例7类似。
实施例8
(E)-7-羟基庚-5-烯-1-基苯甲酸酯：淡黄色油状液体，产率80％。
1H NMR(400MHz,CDCl3):δ8.04(d,J＝7.4Hz,2H),7.55(t,J＝7.4Hz,1H),7.44(t,J＝7.6Hz,2H),5.79-5.58(m,2H),4.32(t,J＝6.6Hz,2H),4.09(d,J＝3.8Hz,2H),2.21-2.06(m,2H),1.86-1.71(m,2H),1.55(dt,J＝14.8,7.5Hz,2H),1.46(s,1H)ppm.13C NMR(100MHz,CDCl3):δ166.70,132.89,132.52,130.42,129.57,128.36,64.85,63.72,31.80,28.23,25.51ppm。
实施例9
(E)-4-羟基丁-2-烯-1-基苯甲酸酯：淡黄色油状液体，产率92％。
1H NMR(400MHz,CDCl3):δ8.05(d,J＝7.3Hz,2H),7.56(t,J＝7.4Hz,1H),7.44(t,J＝7.7Hz,2H),6.12-5.84(m,2H),4.84(d,J＝5.5Hz,2H),4.21(d,J＝4.0Hz,2H),1.70(s,1H)ppm.13C NMR(100MHz,CDCl3):δ166.37,133.51,133.07,130.10,129.65,128.41,125.15,64.70,62.78ppm。
实施例10
(F)-12-羟基十二碳-10-烯-1-基苯甲酸酯：淡黄色油状液体，产率67％。.
1H NMR(400MHz,CDCl3):δ8.04(d,J＝7.5Hz,2H),7.55(t,J＝7.1Hz,1H),7.43(t,J＝7.4Hz,2H),5.82-5.48(m,2H),4.31(t,J＝6.5Hz,2H),4.08(d,J＝4.8Hz,2H),2.03(d,J＝6.5Hz,2H),1.75(dd,J＝13.9,6.8Hz,2H),1.42(d,J＝6.9Hz,3H),1.35(d,J＝5.5Hz,4H),1.29(s,6H)ppm.13C NMR(100MHz,CDCl3):δ166.73,133.47,132.82,130.52,129.54,128.89,128.33,65.14,63.83,32.21,29.64-29.02,28.72,26.03ppm。
实施例11
(E)-4-((4-硝基苯基)氨基)丁-2-烯-1-醇：深黄色油状液体，产率77％。
1H NMR(400MHz,CDCl3):δ8.06(d,J＝9.0Hz,2H),6.53(d,J＝9.1Hz,2H),6.05-5.66(m,2H),4.78(s,1H),4.17(s,2H),3.87(t,J＝5.2Hz,2H),1.72(s,1H)ppm.13C NMR(100MHz,CDCl3):δ153.13,138.11,132.18,126.41,111.28,62.70,44.68ppm。
实施例12
(F)-4-((5-羟基戊-3-烯-1-基)氧基)苯甲酸甲酯：淡黄色油状液体，产率69％。
1H NMR(400MHz,CDCl3):δ7.97(d,J＝8.4Hz,2H),6.89(d,J＝8.4Hz,2H),5.78(s,2H),4.12(s,2H),4.04(t,J＝6.4Hz,2H),3.87(s,3H),2.55(d,J＝4.3Hz,2H),1.74(s,1H)ppm.13C NMR(100MHz,CDCl3):δ166.91,162.63,131.90,131.60,127.76,122.57,114.18,67.39,63.44,51.89,31.99ppm。
实施例13
(E)-5-(2-溴苯氧基)戊-2-烯-1-醇：淡黄色油状液体，产率79％。
1H NMR(400MHz,CDCl3):δ7.54(d,J＝7.9Hz,1H),7.26(q,J＝7.9Hz,2H),7.03(t,J＝7.0Hz,1H),5.74(s,2H),4.11(s,2H),2.99(t,J＝7.2Hz,2H),2.45(s,2H),1.67(s,1H)ppm.13C NMR:(100MHz,CDCl3)δ137.89,133.04,131.87,131.17,129.85,128.08,127.74,126.59,63.41,32.47,31.25ppm。
实施例14
(E)-4-((7-羟基庚-5-烯-1-基)氧基)苄腈：淡黄色油状液体，产率56％。
1H NMR(400MHz,CDCl3):δ7.57(d,J＝8.8Hz,2H),6.92(d,J＝8.8Hz,2H),5.76-5.61(m,2H),4.10(d,J＝4.2Hz,2H),4.00(t,J＝6.4Hz,2H),2.21-2.09(m,2H),1.87-1.77(m,2H),1.60-1.54(m,2H),1.33(s,1H)ppm.13C NMR:(100MHz,CDCl3)δ162.37,133.99,132.40,129.61,119.30,115.17,103.76,68.14,63.69,31.78,28.46,25.43ppm。
Claims (9)
1.一种具有邻位空间位阻结构的钌烯烃复分解催化剂，其特征在于，所述催化剂具有如下结构通式：
其中：通式中的R为甲基、异丙基、叔丁基中的任一种。
2.一种具有邻位空间位阻结构的钌烯烃复分解催化剂的制备方法，其特征在于，包括以下步骤：
(1)将Zn(OAc)2·2H2O和化合物(I)溶于异丙醇溶剂中，再加入乙二胺，搅拌，反应后过滤沉淀的固体，用甲醇和氯仿的混合液进行洗涤，真空干燥得化合物(Ⅱ)；
(2)在氮气条件下，将Grubbs-Hoveyda II和化合物(Ⅱ)加入到干燥的四氢呋喃溶剂中，搅拌，反应后在N2下离心，收集溶液后，将其排干至固体，用无水乙醚洗涤，干燥得本发明钌烯烃复分解催化剂化合物(Ⅲ)；
化合物(I)的化学结构通式为化合物(Ⅱ)的化学结构通式为化合物(Ⅲ)的化学结构通式为
其中：R均为甲基、异丙基、叔丁基中的任一种。
3.根据权利要求2所述一种具有邻位空间位阻结构的钌烯烃复分解催化剂的制备方法，其特征在于，所述步骤(1)中，Zn(OAc)2·2H2O和化合物(I)的摩尔比为1:(0.2-0.4)。
4.根据权利要求2所述一种具有邻位空间位阻结构的钌烯烃复分解催化剂的制备方法，其特征在于，所述步骤(1)中，所述异丙醇的加入量为每1mmol化合物(I)对应加入异丙醇2-3ml，所述乙二胺的加入量为每1mmol化合物(I)对应加入乙二胺0.3-0.4g。
5.根据权利要求2所述一种具有邻位空间位阻结构的钌烯烃复分解催化剂的制备方法，其特征在于，所述步骤(1)中，搅拌温度为18℃-25℃，搅拌时间为0.5-3小时。
6.根据权利要求2所述一种具有邻位空间位阻结构的钌烯烃复分解催化剂的制备方法，其特征在于，所述步骤(1)中，甲醇和氯仿的体积比为1:(1-2)。
7.根据权利要求2至6任一项所述一种具有邻位空间位阻结构的钌烯烃复分解催化剂的制备方法，其特征在于，所述步骤(2)中，Grubbs-Hoveyda II和化合物(Ⅱ)的摩尔比为1:(1-2)。
8.根据权利要求2至6任一项所述一种具有邻位空间位阻结构的钌烯烃复分解催化剂的制备方法，其特征在于，所述步骤(2)中，搅拌温度为4℃-10℃，搅拌时间为1-3小时。
9.一种具有邻位空间位阻结构的钌卡宾催化剂在烯烃复分解反应中的应用。
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