CN113000066B - 一种z-选择性钌卡宾烯烃复分解催化剂及其制备方法和应用 - Google Patents
一种z-选择性钌卡宾烯烃复分解催化剂及其制备方法和应用 Download PDFInfo
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- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 28
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 27
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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Abstract
本发明公开了一种Z‑选择性钌卡宾烯烃复分解催化剂，该催化剂利用溴原子的强拉电子特点，提高催化剂的反应活性；溴原子的加入还加大了整个配体的空间位阻，提高了催化剂的选择性；大空间位阻作用使配合物拥有接近中间过渡态的三角双锥型配位结构，提高了催化剂的催化活性。该催化剂还通过抑制硫原子对苄亚基卡宾碳的亲核加成反应，提高了催化剂的稳定性和耐温性。本发明还公开了该催化剂的制备方法，该方法步骤简单，反应条件温和，得到的催化剂具有优异的热稳定性。本发明还公开了该催化剂在催化钌卡宾烯烃复分解反应制备Z‑式烯烃产物的应用，该催化剂催化烯烃反应可以得到特定构型的顺式产物，具有催化活性高、选择性高、产物收率高的特点。
Description
技术领域
本发明属于过渡金属有机催化剂领域，涉及一种Z-选择性钌卡宾烯烃复分解催化剂及其制备方法和应用。
背景技术
Z-式结构的烯烃在化学、生物和医药等领域具有广泛的应用，其需要通过快速高效和立体选择性的催化反应制备得到，而催化反应的关键是催化剂。很多的天然开链的化合物(比如油酸、亚麻酸)、天然的大环化合物(例如灵猫酮等)、某些据具有抗癌活性的物质中都含有Z-式烯烃结构，但是传统的烯烃复分解催化剂在催化开链烯烃的交叉复分解反应(CM)、形成大环的关环烯烃复分解反应(RCM)中常得到高比例的E-型结构烯烃。因此，如何对催化剂结构进行重塑使其在催化过程当中能够高选择性的得到Z-式烯烃结构产物成为当今烯烃复分解研究领域的热点。
烯烃复分解领域的研究已经取得了突破性的研究成果，但是仍然面临着巨大的困难和挑战。2011年，Grubbs课题组首次报到了一种羧基螯合的Z-选择性钌卡宾烯烃复分解催化剂，首次实现了交叉复分解的Z-式催化。但该类催化剂不稳定，催化活性较低且容易分解。随后的研究中发现，用硝基取代催化剂中的羧基后，催化剂的催化活性和Z-选择性得到大大提高，但是该类催化剂容易分解的问题仍然没有得到解决。Hoveyda课题组在2013年发现当以1,2-苯二硫酚为配体取代化合物中的两个氯原子时，所形成的配合物可催化张力环的开环交叉复分解反应，并得到一定Z式比例的产物。发明人在2019年发现当使用3,4-二巯基-1-环丁烯-1,2-二酮替代2,5-二氯苯二巯基后催化剂表现出极好的稳定性，即使在空气中也能长时间保存。在我们随后的研究中发现的1,8-萘二巯基螯合的催化剂具有非常高的Z-选择性，但是催化活性较低。
由上述可知，现有技术存在以下不足：虽然Z-选择性烯烃复分解催化剂的研究已经取得了一些成果，但是仍为发现有普遍的规律可循；此类催化剂种类较少，且报道出的催化剂选择性和活性有待进一步提高。硝基螯合的六配位Grubbs型催化剂的催化活性和选择性较高，但合成过程较为复杂，稳定性较差，官能团适用性不高。而刚刚兴起的含有双硫螯合配体类的钌卡宾催化剂，其合成过程简单，具有较好的官能团适用性，拥有巨大的应用前景。但是，双硫螯合配体类的钌卡宾催化剂的活性、Z-选择性尚需进一步优化。
发明内容
为了克服现有技术的不足，本发明的目的之一在于提供一种Z-选择性钌卡宾烯烃复分解催化剂，该催化剂在催化钌卡宾烯烃复分解反应中具备较高的Z-式选择性、稳定性更好、催化效率更高的特点。
本发明的目的之二在于提供一种Z-选择性钌卡宾烯烃复分解催化剂的制备方法。
本发明的目的之三在于提供Z-选择性钌卡宾烯烃复分解催化剂在催化钌卡宾烯烃复分解反应制备Z-式烯烃产物的应用。
本发明的目的之一在于采用如下技术方案实现：
一种Z-选择性钌卡宾烯烃复分解催化剂，具有结构通式Ⅰ：
其中Mes为2,4,6-三甲基苯基。
本发明的目的之二采用如下技术方案实现：
上述Z-选择性钌卡宾烯烃复分解催化剂的制备方法，包括以下步骤：
其中：
氮气条件下，将Hoveyda催化剂(A)与2,4,5,7-四溴-1,8-二巯基锌盐(B)或2,4,5,7-四溴-1,8-双硫代酸钠(C)溶于有机溶剂中，搅拌后真空干燥，加入二氯甲烷后离心，除去溶剂即得最终产物Ⅰ，即2,4,5,7-四溴-1,8-萘二疏基钌卡宾化合物。
进一步地，所述有机溶剂为四氢呋喃。
进一步地，所述搅拌温度为0℃，时间0.5h。
优选地，化合物B和化合物C的合成步骤为：
化合物1-4的合成参照文献：R.J.Wright,C.Lim,T.D.Tilley,Chem.Eur.J.2009,15,8518。
在氮气保护下，取化合物3(505.6mg，1mmol)溶于20mL四氢呋喃中，0℃下缓慢加入LiAlH4(114.0mg，3mmol)反应1h。反应结束后加入1M HCl(10mL)，用氯仿萃取、无水硫酸钠干燥，除去溶剂后得到化合物4(219.3mg,0.43mmol)。
将化合物4(507.6mg,1mmol)、Zn(OAc)2·2H2O(876.9mg,4mmol,4.0equiv)、乙二胺(0.40mL,6mmol,6.00equiv.)放入25mL圆底烧瓶中，加入10mL异丙醇，在室温下搅拌2h。过滤得到固体沉淀物，分别用甲醇(5mL洗3次)和氯仿(5mL洗3次)洗涤。抽干后得到黄色固体化合物B(415.8mg，0.73mmol)。
将化合物4(507.6mg,1mmol)和叔丁醇钠(107.9mg，1.1equiv.)溶于10mL甲醇中，搅拌20min后旋干，用石油醚洗涤，得到黄色化合物C(518.5mg，0.94mmol)。
本发明的目的之三采用如下技术方案实现：
上述Z-选择性钌卡宾烯烃复分解催化剂在催化钌卡宾烯烃复分解反应制备Z-式烯烃产物的应用。
相比现有技术，本发明的有益效果在于：
1.本发明提供了一种Z-选择性钌卡宾烯烃复分解催化剂，利用2,4,5,7-四溴-1,8-萘二疏基中溴原子的强拉电子特点，降低金属钌中心的电子云密度，使其更易与烯烃配位，提高生成金属四元环过渡态的速率，进而提高催化剂的反应活性。
本发明提供的催化剂通过抑制硫原子对苄亚基卡宾碳的亲核加成反应，提高配合物的稳定性和耐温性；同时溴原子的加入可加大整个配体的空间位阻，进而提高催化剂的选择性。
本发明利用2,4,5,7-四溴-1,8-萘二疏基配体的大空间位阻作用，使其与氮杂环卡宾配体之间的排斥力增加，从而迫使配体尽量远离同样拥有大空间阻碍的氮杂环卡宾配体，使配合物拥有接近中间过渡态的三角双锥型配位结构，提高了催化剂的催化活性；配体的大空间阻碍作用也会使配合物在反应过程中产生的过渡态具有更为紧凑的空间环境，进而提高四元环过渡态中的对取代基团的立体控制能力。
2.本发明还提供了该催化剂的制备方法，该方法步骤简单，反应条件温和，制备得到的产物具有优异的热稳定性。
3.本发明还提供了该催化剂在催化钌卡宾烯烃复分解反应制备Z-式烯烃产物的应用，该催化剂催化烯烃反应可以得到特定构型的顺式产物，具有催化活性高、Z-式选择性高、产物收率高的特点。
附图说明
图1为本发明催化剂热稳定性测试结果图。
具体实施方式
下面，结合具体实施方式及附图对本发明做进一步描述，需要说明的是，在不相冲突的前提下，以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。
实施例1
一种Z-选择性钌卡宾烯烃复分解催化剂，具有结构通式Ⅰ，制备过程如下：氮气保护下，在10mL圆底烧瓶中，将Hoveyda催化剂A(187.5mg,2.4mmol)与2,4,5,7-四溴-1,8-二疏基锌盐B(236.0mg,0.4mmol)溶于5mL四氢呋喃中，0℃下搅拌0.5h，反应结束后真空干燥，加入二氯甲烷后离心，除去溶剂后得到棕黄色固体粉末，即最终产物Ⅰ(196.4mg，收率74.1％)。
1H NMR(400MHz,CDCl3)δ15.38(s,1H),7.32(d,J＝13.6Hz,2H),7.04–6.91(m,3H),6.85–6.67(m,3H),3.99(d,J＝7.6Hz,3H),2.61–2.39(m,9H),2.21(t,J＝26.3Hz,9H),1.80(d,J＝6.7Hz,4H),1.51(d,J＝6.6Hz,3H).13C NMR(101MHz,CDCl3)δ153.99,142.31,141.42,140.93,135.26,132.32,131.32,131.18,129.50,129.22,127.34,126.40,124.29,124.01,122.69,122.01,115.59,80.77,53.63,51.43,24.33,21.58,21.18,19.23ppm.ESI-MS[M]+calcd for C41H41Br4N2ORuS2:1061.8318；found:1061.8346.
实施例2
实施例2与实施例1的区别在于：将2,4,5,7-四溴-1,8-双硫代酸钠(C)替换2,4,5,7-四溴-1,8-二疏基锌盐(B),其余与实施例1相同，得到最终产物Ⅰ(145.6mg，收率54.9％)。
1H NMR(400MHz,CDCl3)δ15.38(s,1H),7.32(d,J＝13.6Hz,2H),7.04–6.91(m,3H),6.85–6.67(m,3H),3.99(d,J＝7.6Hz,3H),2.61–2.39(m,9H),2.21(t,J＝26.3Hz,9H),1.80(d,J＝6.7Hz,4H),1.51(d,J＝6.6Hz,3H).13C NMR(101MHz,CDCl3)δ153.99,142.31,141.42,140.93,135.26,132.32,131.32,131.18,129.50,129.22,127.34,126.40,124.29,124.01,122.69,122.01,115.59,80.77,53.63,51.43,24.33,21.58,21.18,19.23ppm.
实验例1
催化生成：((Z)-2-((1’S,3’R)-3’-乙烯基环戊基)乙烯基)苯
氮气保护下，将14.3mg(0.15mmol)降冰片烯和312.3mg(3mmol)苯乙烯加入反应试管中，接着加入溶有4.8mg(4.5μmol,3.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在室温下搅拌4h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物28.1mg(产率95.0％)，Z/E为98:2。
1H NMR(600MHz,CDCl3)：δ7.36–7.31(m,2H),7.28–7.21(m,3H),6.37(d,J＝11.5Hz,1H),5.83(ddd,J＝17.4,10.2,7.4Hz,1H),5.59(dd,J＝11.5,10.0Hz,1H),5.00(ddd,J＝17.1,2.0,1.2Hz,1H),4.91(ddd,J＝10.2,1.9,1.0Hz,1H),3.20–2.90(m,1H),2.67–2.43(m,1H),2.15–2.00(m,1H),1.97–1.80(m,2H),1.63–1.46(m,2H),1.24(dt,J＝12.5,10.4Hz,1H).13C NMR(151MHz,CDCl3)δ143.15,138.05,137.92,128.71,128.24,127.72,126.59,112.66,44.65,41.55,38.79,33.13,32.04ppm.
实验例2
催化生成：(Z)-1-氟-4-(2-((1’S,3’R)3’-乙烯基环戊基)乙烯基)苯
氮气保护下，将14.3mg(0.15mmol)降冰片烯和366.2mg(3mmol)4-氟苯乙烯加入反应试管中，接着加入溶有4.8mg(4.5μmol,3.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在室温下搅拌4h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物30.2mg(产率93.0％)，Z/E为99:1。
1H NMR(600MHz,CDCl3)δ7.22–7.18(m,2H),7.03–6.96(m,2H),6.31(d,J＝11.5Hz,1H),5.82(ddd,J＝17.4,10.2,7.4Hz,1H),5.56(dd,J＝11.5,10.0Hz,1H),4.99(ddd,J＝17.1,1.9,1.2Hz,1H),4.90(ddd,J＝10.2,1.9,1.0Hz,1H),2.99(ddd,J＝4.6,2.6,1.3Hz,1H),2.68–2.45(m,1H),2.00(tdd,J＝6.6,6.1,1.2Hz,1H),1.93–1.76(m,2H),1.59–1.45(m,2H),1.22(dt,J＝12.5,10.4Hz,1H)..13C NMR(151MHz,CDCl3)δ162.42,160.80,143.02,137.97,133.88,133.86,130.21,130.16,126.60,115.15,115.01,112.71,44.62,41.45,38.64,33.06,32.00ppm.
实验例3
催化生成：(3-(Z)-苯乙烯基-5-乙烯基)环戊烷-1,2-二甲醇
氮气保护下，将23.1mg(0.15mmol)降冰片烯二甲醇和312.3mg(3mmol)苯乙烯加入反应试管中，接着加入溶有4.8mg(4.5μmol,3.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在室温下搅拌4h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物34.5mg(产率89％)，Z/E为97:3。
1H NMR(600MHz,CDCl3)δ7.34–7.27(m,2H),7.25–7.16(m,3H),6.46(d,J＝11.5Hz,1H),5.73(ddd,J＝17.0,10.1,7.8Hz,1H),5.51(dd,J＝11.5,10.0Hz,1H),5.11–4.88(m,2H),4.10–3.77(m,2H),3.66–3.55(m,3H),3.50(dd,J＝11.5,2.8Hz,1H),2.79–2.61(m,1H),2.21–2.12(m,1H),2.10(dd,J＝8.5,4.0Hz,2H),1.98(dt,J＝12.3,6.0Hz,1H),1.35(dt,J＝12.4,11.0Hz,1H).13C NMR(151MHz,CDCl3)δ141.46,137.53,135.90,129.86,128.59,128.39,126.82,114.63,61.93,50.50,48.52,46.42,40.25,39.85ppm.
实验例4
催化生成：(3-(Z)-4-氟苯乙烯基-5-乙烯基)环戊烷-1,2-二甲醇
氮气保护下，将23.1mg(0.15mmol)降冰片烯二甲醇和366.2mg(3mmol)4-氟苯乙烯加入反应试管中，接着加入溶有4.8mg(4.5μmol,3.0mol％)实施例1得到的催化剂的1mLTHF(四氢呋喃)溶液中，在室温下搅拌4h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物38.9mg(产率94％)，Z/E为98:2。
1H NMR(600MHz,CDCl3)δ7.20–7.14(m,2H),7.03–6.94(m,2H),6.40(d,J＝11.5Hz,1H),5.72(ddd,J＝17.0,10.1,7.9Hz,1H),5.49(dd,J＝11.5,10.1Hz,1H),4.97(dddd,J＝23.1,10.1,1.8,0.8Hz,2H),3.79(s,2H),3.66–3.47(m,4H),2.71–2.57(m,1H),2.25–2.13(m,1H),2.12–2.07(m,2H),2.01–1.92(m,1H),1.33(dt,J＝12.4,11.2Hz,1H).13C NMR(151MHz,CDCl3)δ162.50,160.87,141.35,135.92,133.51,133.48,130.17,130.12,128.75,115.33,115.18,114.70,61.88,50.46,48.49,46.38,40.15,39.78ppm.
实验例5
催化生成：(Z)-4-羟基-2-丁烯-1-苯甲酸酯
氮气保护下，19.4mg(0.12mmol)苯甲酸丙烯酯和22.4mg(0.24mmol)Z-丁烯-1,4-二醇，接着加入溶有6.4mg(6.0μmol,5.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在60℃下搅拌6h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物18.1mg(产率78.7％)，Z/E为98:2。
1H NMR(600MHz,CDCl3)δ8.02(ddd,J＝4.4,2.4,1.2Hz,2H),7.71–7.50(m,1H),7.49–7.31(m,2H),6.01–5.83(m,1H),5.79–5.59(m,1H),4.92(dd,J＝7.0,1.3Hz,2H),4.32(dd,J＝7.1,3.0Hz,2H),2.16(s,1H).13C NMR(151MHz,CDCl3)δ166.76,133.65,133.21,130.11,129.73,128.49,125.71,60.68,58.62ppm.
实验例6
催化生成：(Z)-7-羟基-5-庚烯-1-苯甲酸酯
氮气保护下，24.5mg(0.12mmol)苯甲酸丙烯酯和22.4mg(0.24mmol)Z-丁烯-1,4-二醇，接着加入溶有6.4mg(6.0μmol,5.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在60℃下搅拌6h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物23.6mg(产率84.0％)，Z/E为97:3。
1H NMR(400MHz,CDCl3)δ8.10–7.99(m,2H),7.56(ddd,J＝6.9,4.1,1.4Hz,1H),7.50–7.36(m,2H),5.64(dddd,J＝9.4,6.5,4.7,3.2Hz,1H),5.58–5.43(m,1H),4.33(t,J＝6.6Hz,2H),4.21(d,J＝6.6Hz,2H),2.17(qd,J＝7.4,1.4Hz,2H),1.84–1.72(m,2H),1.60(s,1H),1.58–1.50(m,2H).13C NMR(151MHz,CDCl3)δ166.80,132.99,132.28,130.45,129.63,129.21,128.44,64.84,58.60,28.29,27.02,26.00ppm.
实验例7
催化生成：(Z)-12-羟基-10-十二烷烯-1-苯甲酸酯
氮气保护下，32.9mg(0.12mmol)苯甲酸丙烯酯和22.4mg(0.24mmol)Z-丁烯-1,4-二醇，接着加入溶有6.4mg(6.0μmol,5.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在60℃下搅拌6h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物30.3mg(产率84.0％)，Z/E为98:2。
1H NMR(400MHz,CDCl3)δ8.21–7.87(m,2H),7.76–7.53(m,1H),7.49–7.32(m,2H),5.64–5.57(m,1H),5.57–5.49(m,1H),4.31(t,J＝6.7Hz,2H),4.19(d,J＝6.3Hz,2H),2.07(q,J＝7.0Hz,2H),1.83–1.70(m,2H),1.44(s,1H),1.38–1.27(m,12H).13C NMR(101MHz,CDCl3)δ166.71,133.21,132.79,130.56,129.54,128.38,128.32,65.12,58.63,29.58,29.43,29.37,29.23,29.16,28.72,27.42,26.01ppm.
实验例8
催化生成：(Z)-5-(4’-硝基苯氧基)-2-戊烯-1-醇
氮气保护下，23.1mg(0.12mmol)苯甲酸丙烯酯和22.4mg(0.24mmol)Z-丁烯-1,4-二醇，接着加入溶有6.4mg(6.0μmol,5.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在60℃下搅拌6h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物21.7mg(产率81.2％)，Z/E为92:8。
1H NMR(400MHz,CDCl3)δ8.21(dd,J＝9.4,2.7Hz,2H),7.08–6.79(m,2H),5.98–5.88(m,1H),5.83(dd,J＝12.4,6.2Hz,1H),4.75(d,J＝6.0Hz,2H),4.37–4.25(m,2H),1.53(d,J＝24.1Hz,2H),1.26(d,J＝2.7Hz,1H).13C NMR(101MHz,CDCl3)δ163.80,141.58,131.74,127.43,125.94,125.92,114.45,67.91,58.44,27.37ppm.
实验例9
催化生成：(Z)-7-(4’-硝基苯氧基)-2-庚烯-1-醇
氮气保护下，26.5mg(0.12mmol)苯甲酸丙烯酯和22.4mg(0.24mmol)Z-丁烯-1,4-二醇，接着加入溶有6.4mg(6.0μmol,5.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在60℃下搅拌6h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物26.2mg(产率86.9％)，Z/E为91:9。
1H NMR(400MHz,CDCl3)δ8.59–8.00(m,1H),7.18–6.82(m,2H),5.77–5.64(m,1H),5.63–5.52(m,1H),4.24(d,J＝6.6Hz,2H),4.07(t,J＝6.4Hz,2H),2.23–2.14(m,2H),1.92–1.80(m,2H),1.65–1.53(m,2H),1.32(s,1H).13C NMR(101MHz,CDCl3)δ164.11,132.28,129.10,125.93,114.39,68.59,58.57,28.50,27.02,25.93ppm.
实验例10
催化生成：(Z)-2-(5’-羟基-3’-戊烯基)-异吲哚啉-1,3-二酮
氮气保护下，24.1mg(0.12mmol)苯甲酸丙烯酯和22.4mg(0.24mmol)Z-丁烯-1,4-二醇，接着加入溶有6.4mg(6.0μmol,5.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在60℃下搅拌6h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物23.2mg(产率83.5％)，Z/E为95:5。
1H NMR(400MHz,CDCl3)δ7.87(dd,J＝5.4,3.1Hz,2H),7.74(dd,J＝5.5,3.0Hz,2H),5.87–5.65(m,1H),5.64–5.37(m,1H),4.17(t,J＝5.1Hz,2H),3.79(t,J＝7.1Hz,2H),2.53(qd,J＝7.4,1.5Hz,2H),1.47(s,1H).13C NMR(101MHz,CDCl3)δ168.40,133.99,132.04,131.70,127.99,123.26,58.32,37.49,26.54ppm.
实验例11
催化生成：(Z)-2-(7’-羟基-5’-庚烯基)-异吲哚啉-1,3-二酮
氮气保护下，27.5mg(0.12mmol)苯甲酸丙烯酯和22.4mg(0.24mmol)Z-丁烯-1,4-二醇，接着加入溶有6.4mg(6.0μmol,5.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在60℃下搅拌6h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物27.9mg(产率89.6％)，Z/E为98:2。
1H NMR(400MHz,CDCl3)δ7.86(dd,J＝5.4,3.1Hz,2H),7.77–7.64(m,2H),5.71–5.60(m,1H),5.58–5.38(m,1H),4.23(d,J＝6.8Hz,2H),3.75–3.65(m,2H),2.18(qd,J＝7.4,1.5Hz,2H),1.77–1.65(m,2H),1.47(p,J＝7.3Hz,2H).13C NMR(101MHz,CDCl3)δ169.18,134.63,132.84,129.90,123.93,59.20,38.29,28.46,27.26,27.10ppm.
实验例12
催化生成：(Z)-4-(7’-羟基-5’-庚烯-1’-氧基)苯甲醛
氮气保护下，24.1mg(0.12mmol)苯甲酸丙烯酯和22.4mg(0.24mmol)Z-丁烯-1,4-二醇，接着加入溶有6.4mg(6.0μmol,5.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在60℃下搅拌6h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物24.3mg(产率86.4％)，Z/E为97:3。
1H NMR(400MHz,CDCl3)δ9.88(d,J＝8.9Hz,1H),8.23–7.68(m,2H),6.99(dd,J＝8.8,2.2Hz,2H),5.78–5.62(m,1H),5.60–5.49(m,1H),4.22(t,J＝5.6Hz,2H),4.04(t,J＝6.3Hz,2H),2.17(q,J＝7.3Hz,2H),1.88–1.78(m,2H),1.62–1.49(m,2H).13C NMR(101MHz,CDCl3)δ190.89,164.17,132.23,132.03,129.81,129.11,114.75,68.13,58.52,28.56,27.05,25.98ppm.
实验例13
催化生成：4-[(3’Z)-5’-羟基-3’-戊烯-1’-氧基]苯甲酸甲酯
氮气保护下，24.7mg(0.12mmol)苯甲酸丙烯酯和22.4mg(0.24mmol)Z-丁烯-1,4-二醇，接着加入溶有6.4mg(6.0μmol,5.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在60℃下搅拌6h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物24.0mg(产率84.7％)，Z/E为98:2。
1H NMR(400MHz,CDCl3)δ8.15–7.84(m,2H),7.05–6.81(m,2H),5.97–5.77(m,1H),5.76–5.49(m,1H),4.26(d,J＝6.6Hz,2H),4.06(t,J＝6.4Hz,2H),3.90(s,3H),2.75–2.55(m,2H),1.61(s,1H).13C NMR(101MHz,CDCl3)δ166.86,162.45,131.63,131.48,128.01,122.75,114.05,67.15,58.39,51.90,27.46ppm.
实验例14
催化生成：4-[(5’Z)-7’-羟基-3’-庚烯-1-氧基]苯甲酸甲酯
氮气保护下，28.1mg(0.12mmol)苯甲酸丙烯酯和22.4mg(0.24mmol)Z-丁烯-1,4-二醇，接着加入溶有6.4mg(6.0μmol,5.0mol％)实施例1得到的催化剂的1mL THF(四氢呋喃)溶液中，在60℃下搅拌6h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-60％乙酸乙酯的石油醚溶液)，最终得到无色的油状物24.5mg(产率77.4％)，Z/E为96:4。
1H NMR(400MHz,CDCl3)δ8.25–7.85(m,2H),6.99–6.82(m,2H),5.73–5.64(m,1H),5.58(dt,J＝11.0,7.2Hz,1H),4.23(d,J＝6.6Hz,2H),4.03(t,J＝6.4Hz,2H),3.90(s,3H),2.19(q,J＝7.4Hz,2H),1.83(dd,J＝9.0,6.2Hz,2H),1.62–1.50(m,2H),1.36(s,1H).13CNMR(101MHz,CDCl3)δ166.92,162.85,132.33,131.59,129.04,122.44,114.06,67.90,58.55,51.84,28.63,27.08,26.02ppm.
实验例15
催化剂热稳定性测试
将本发明得到的催化剂Ⅰ与发明人之前的报道催化剂D和E在相同条件下做热稳定性测试，即以蒽为内标，55℃下使用1H NMR监测了催化剂I、D、E在THF-d8中的分解情况。其中催化剂D和E的结构式分别为:
催化剂D、E和I均取9.8mg装入核磁管中，然后加入3.6mg(0.02mmol)内标物蒽，再向核磁管中加入0.5mL的无水氘代四氢呋喃(THF-d8)。在55℃温度下，在布鲁克核磁仪中每隔30min连续测试三种催化剂的氢谱。通过监测卡宾碳上氢原子的和内标物的峰面积来确定催化剂的分解速率。
结果如图1所示：本发明得到的催化剂Ⅰ相对于催化剂D、E分解速率最慢，表明本发明得到的催化剂Ⅰ的热稳定性得到大大提高。
综上，本发明提供的2,4,5,7-四溴-1,8-萘二疏基钌卡宾催化剂在催化烯烃复分解反应中得到的产物Z/E比例高达99:1，产率高达95％，具有稳定性好、反应活性高、Z-式选择性强、收率高的特点。克服了目前现有技术中有关Z-选择性烯烃复分解催化研究中催化剂活性低、Z-选择性差等缺点，具有良好的应用前景。
上述实施方式仅为本发明的优选实施方式，不能以此来限定本发明保护的范围，本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
Claims (4)
1.一种Z-选择性钌卡宾烯烃复分解催化剂的制备方法，其特征在于，包括以下步骤：
其中： 
氮气条件下，将Hoveyda催化剂(A)与2,4,5,7-四溴-1,8-二巯基锌盐(B)或2,4,5,7-四溴-1,8-双硫代酸钠(C)溶于有机溶剂中，搅拌后真空干燥，加入二氯甲烷后离心，除去溶剂即得最终产物——Z-选择性钌卡宾烯烃复分解催化剂，该最终产物具有结构通式Ⅰ；
其中Mes为2,4,6-三甲基苯基。
2.如权利要求1所述的Z-选择性钌卡宾烯烃复分解催化剂的制备方法，其特征在于，所述有机溶剂为四氢呋喃。
3.如权利要求1所述的Z-选择性钌卡宾烯烃复分解催化剂的制备方法，其特征在于，所述搅拌温度为0 oC，时间0.5 h。
4.如权利要求1所述方法制备得到的Z-选择性钌卡宾烯烃复分解催化剂在催化钌卡宾烯烃复分解反应制备Z-式烯烃产物的应用。
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