CN108659049B - Z-选择性钌烯烃复分解催化剂及制备方法及应用 - Google Patents

Z-选择性钌烯烃复分解催化剂及制备方法及应用 Download PDF

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CN108659049B
CN108659049B CN201710198126.8A CN201710198126A CN108659049B CN 108659049 B CN108659049 B CN 108659049B CN 201710198126 A CN201710198126 A CN 201710198126A CN 108659049 B CN108659049 B CN 108659049B
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王建辉
王涛
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Abstract

本发明公开了Z‑选择性钌烯烃复分解催化剂及制备方法及应用，该催化剂用式(I)所示：
Figure DDA0001257909640000011
其中：Mes为2,4,6‑三甲基苯基；X为氧或硫。本发明的方法步骤简单，所需条件温和，室温即可反应，并且能得到特定构型的顺式产物。本发明的催化剂与目前最好的顺式烯烃复分解催化剂VI相比具有更好的热稳定性与催化活性。Z‑选择性钌烯烃复分解催化剂催化烯烃复分解反应产生Z‑式烯烃产物。

Description

Z-选择性钌烯烃复分解催化剂及制备方法及应用
技术领域
本发明属过渡金属有机催化剂领域，涉及一种稳定的Z-选择性钌烯烃复分解催化剂及制备方法及应用。
背景技术
目前，烯烃复分解研究领域中最具挑战性的问题是如何通过烯烃复分解反应产生Z-式烯烃产物。这主要是由于天然开链的化合物(比如油酸、亚麻酸)，天然的大环化合物(比如灵猫酮)等等，某些具有抗癌活性的物质中也含有Z式烯烃结构。而常用的烯烃复分解催化剂在开链烯烃的交叉复分解反应、形成大环产物的关环烯烃复分解反应中常给出高比例的E-型异构体。因此，如何重新设计催化剂的结构，使其在催化烯烃反应过程中高选择性地产生Z式烯烃是当前烯烃复分解领域中最具有挑战性的热门研究课题。例如，2011年Grubbs课题组首次报到了一种Z-选择性的钌卡宾烯烃复分解催化剂，引起人们的高度关注(1)。这种催化剂含有一个具有碳负离子的N-杂环卡宾配合物(NHC)双齿结构的配体。经过进一步研究发现此类催化剂可以催化末端烯烃交叉复分解反应，并且具有较好的官能团适用性，在不同的溶剂和温度条件下能够高效的转化烯烃，同时保持优良的Z选择性，其研究进一步拓展了Z-选择性烯烃复分解催化剂的应用范围(2)。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配体时，所形成的配合物可催化张力环的开环移位复分解反应，并给出一定Z-选择性的产物(3)。对比研究发现1,2-苯二酚配位的化合物也能催化烯烃复分解反应，但不具有Z/E选择性。原因是该配合物与卤代溶剂作用生成不具有选择性的卤代催化剂。2015年，Hoveyda等人在《自然》杂志上发表进一步研究结果，当苯二硫酚配体带有卤素取代基时，可增加催化剂的稳定性，同时提高催化活性(4)。催化剂具有良好的官能团适用性，即使烯丙醇类的化合物也不需要保护，可直接进行反应，并且转化率和Z-选择性都较高。
虽然Z-选择性烯烃复分解催化剂的研究虽然已经取得了一些成功，但还没有普遍的规律可循；此类催化剂种类较少，而且催化剂的选择性有待进一步提高。
发明内容
本发明的目的是克服现有技术的不足，提供一种Z-选择性钌烯烃复分解催化剂。
本发明的第二个目的是提供一种Z-选择性钌烯烃复分解催化剂的制备方法。
本发明的第三个目的是提供Z-选择性钌烯烃复分解催化剂的应用。
本发明的技术方案概述如下：
Z-选择性钌烯烃复分解催化剂，用式I所示：
Figure BDA0001257909620000021
其中：Mes为2,4,6-三甲基苯基；X为氧或硫。
Z-选择性钌烯烃复分解催化剂的制备方法，包括如下步骤：
氮气条件下，将Hoveyda-Grubbs II催化剂(II)与碳硼烷二巯基锌盐(III)或碳硼烷二巯基钠盐(IV)溶于干燥的有机溶剂中，室温下搅拌，抽干有机溶剂，加入二氯甲烷后离心，收集上层清液，干燥得化合物Ia，所述有机溶剂为四氢呋喃、二氯甲烷或甲苯；反应式为：
Figure BDA0001257909620000022
其中：
Figure BDA0001257909620000023
或：
氮气条件下，将Hoveyda-Grubbs II催化剂(II)与碳硼烷二羟基钠盐(V)溶于干燥的有机溶剂中，室温下搅拌，抽干有机溶剂，加入二氯甲烷后离心，收集上层清液，干燥得化合物Ib，所述有机溶剂为四氢呋喃、二氯甲烷或甲苯；反应式为：
Figure BDA0001257909620000031
其中：
Figure BDA0001257909620000032
上述Z-选择性钌烯烃复分解催化剂在催化烯烃复分解反应产生Z-式烯烃产物中的应用。
本发明的优点:
本发明的方法步骤简单，所需条件温和，室温即可反应，并且能得到特定构型的顺式产物。本发明与目前最好的顺式烯烃复分解催化剂VI相比具有更好的热稳定性与催化活性。Z-选择性钌烯烃复分解催化剂能催化烯烃复分解反应产生Z-式烯烃产物。
Figure BDA0001257909620000033
附图说明
图1为Z-选择性钌烯烃复分解催化剂Ia及催化剂VI的稳定性测试。
具体实施方式
下面通过具体实施例对本发明作进一步的说明。
化合物(III)(IV)(V)；的来源。
化合物(VII)和(VIII)可根据参考文献(5)和(6)进行合成，合成简单，此处不再赘述。
Figure BDA0001257909620000041
化合物(III)的制备：
由化合物(VII)(1equiv.)，Zn(OAc)2·2H2O(4.00equiv.)和乙二胺(6.00equiv.)在异丙醇中室温下搅拌2小时。过滤得到白色固体，固体分别用甲醇和热氯仿洗，固体抽干得到化合物(III)。
化合物(IV)的制备：
由化合物(VII)(1equiv.)溶于甲苯中滴加到叔丁醇钠(2.2equiv.)的甲醇溶液中，50℃下搅拌2小时。反应结束后，过滤得到白色固体，固体用四氢呋喃洗，固体抽干得到化合物(IV)。
化合物(V)的制备：
由化合物(VIII)(1equiv.)溶于甲苯中滴加到叔丁醇钠(2.2equiv.)的甲醇溶液中，50℃下搅拌2小时。反应结束后，过滤得到白色固体，固体用四氢呋喃洗，固体抽干得到化合物(V)。
实施例1
Z-选择性钌烯烃复分解催化剂的制备方法，包括如下步骤：
氮气保护下，在50mL圆底烧瓶中，将Hoveyda-Grubbs II催化剂II(1.2520g，2mmol)，与碳硼烷二巯基二钠盐IV(0.7204g，3mmol)溶于25mL干燥的四氢呋喃中，室温下搅拌5h，抽干四氢呋喃，加入二氯甲烷后离心，收集上层清液，干燥得到深黄色固体粉末Ia(0.6782g，44.5％)。
经检测，1HNMR(400MHz,CDCl3)：δ15.55(s,1H),7.32–7.27(m,1H),7.12(d,J＝6.1Hz,2H),7.01(d,J＝8.3Hz,1H),6.88(s,1H),6.82(t,J＝7.4Hz,1H),6.71(d,J＝6.6Hz,1H),5.95(s,1H),5.16–5.02(m,1H),3.96(dd,J＝22.1,10.7Hz,2H),3.73(t,J＝9.8Hz,2H),2.63–1.41(m,34H).13C NMR(101MHz,CDCl3)：δ267.65–251.32(m,1H),214.90(s,-1H),138.37(s,2H),134.51(s,1H),130.88(s,1H),129.16(s,5H),128.06(s,2H),123.83(s,1H),122.12(s,2H),115.66(s,1H),83.26(s,2H),53.45(s,1H),51.84(s,2H),51.21(s,1H),23.92(s,2H),21.19(d,J＝20.1Hz,3H),20.28(s,1H),19.17(s,1H),18.26(s,2H),17.06(s,1H).
结构用Ia所示。
Figure BDA0001257909620000051
有机溶剂还可以选用二氯甲烷或甲苯。
用碳硼烷二羟基钠盐V替代本实施例的碳硼烷二巯基二钠盐IV，其它同本实施例，经检测得到深黄色固体粉末Ib(0.8648g，59％)。
Figure BDA0001257909620000052
实施例2
Z-选择性钌烯烃复分解催化剂的制备方法，包括如下步骤：
氮气保护下，在50mL圆底烧瓶中，将Hoveyda-Grubbs II催化剂II(1.2520g，2mmol)，与碳硼烷二巯基二锌盐III(1.0849g，4mmol)溶于25mL干燥的四氢呋喃中，室温下搅拌5h，抽干四氢呋喃，加入二氯甲烷后离心，收集上层清液，干燥得到深黄色固体粉末，经检测为化合物Ia(310g，41.4％)。
催化实验1
催化生成：Z-1-(4-羟基-3-(4-羟基-2-丁烯基)苯基)乙酮
氮气保护下，将26.4mg(0.15mmol)3’-烯丙基-4’-羟基苯乙酮和26.4mg(0.30mmol)Z-1,4-丁烯二醇加入反应试管中。向其中加入1mL含有6.1mg(8μmol)催化剂Ia的THF溶液，在60℃下搅拌8h。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)。
得到灰白色的固体21.2mg(产率68.2％)，Z/E为99：1。1H NMR(600MHz,CDCl3)：δ7.79(d,J＝2.0Hz,1H),7.74(dd,J＝8.4,2.1Hz,1H),6.84(d,J＝8.4Hz,1H),5.77(dd,J＝11.6,5.5Hz,1H),5.67(dd,J＝18.6,8.0Hz,1H),4.36(d,J＝6.5Hz,2H),3.52(d,J＝7.9Hz,2H),2.54(d,J＝6.8Hz,3H),1.36–1.19(m,1H).
催化实验2
催化生成：Z-3-苯基-2-丙烯-1-醇
氮气保护下，将15.6mg(0.15mmol)苯乙烯和52.8mg(0.60mmol)Z-1,4-丁烯二醇加入反应试管中。向其中加入1mL含有6.1mg(8μmol)催化剂Ia的THF溶液，在60℃下搅拌8h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-40％乙酸乙酯的石油醚溶液)。
得到黄色油状液体10.0mg(产率50.1％)，Z/E为97：3。1H NMR(400MHz,CDCl3)：δ7.37(t,J＝7.4Hz,2H),7.32–7.27(m,1H),7.24(d,J＝7.3Hz,2H),6.60(d,J＝11.7Hz,1H),5.95–5.85(m,1H),4.47(dd,J＝6.4,1.4Hz,2H),1.64(s,2H).
催化实验3
催化生成：Z-1,4-丁烯二醇-1-苯甲酸酯
氮气保护下，将24.3mg(0.15mmol)苯甲酸丙烯醇酯和26.4mg(0.30mmol)Z-1,4-丁烯二醇加入反应试管中。向其中加入1mL含有6.1mg(8μmol)催化剂Ia的THF溶液，在60℃下搅拌8h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-40％乙酸乙酯的石油醚溶液)。
得到黄色油状液体20.7mg(产率73.0％)，Z/E为97：3。1H NMR(400MHz,CDCl3)δ8.06(d,J＝7.7Hz,2H),7.59(t,J＝7.4Hz,1H),7.46(t,J＝7.7Hz,2H),5.96(ddd,J＝17.7,12.7,6.9Hz,1H),5.84–5.62(m,1H),4.96(d,J＝7.0Hz,2H),4.36(d,J＝6.5Hz,2H),2.16(s,1H).
催化实验4
催化生成：Z-7-邻苯二甲酰亚胺基-2-庚烯-1-醇
氮气保护下，将34.4mg(0.15mmol)6-邻苯二甲酰亚胺基-1-己烯和26.4mg(0.30mmol)Z-1,4-丁烯二醇加入反应试管中。向其中加入1mL含有6.1mg(8μmol)催化剂Ia的THF溶液，在60℃下搅拌8h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-40％乙酸乙酯的石油醚溶液)。
得到黄色油状液体27.4mg(产率70.4％)，Z/E为98：2。1HNMR(600MHz,CDCl3)δ7.84(dd,J＝5.4,3.1Hz,2H),7.72(dd,J＝5.4,3.0Hz,2H),5.70–5.59(m,1H),5.55–5.43(m,1H),4.21(d,J＝6.8Hz,2H),3.75–3.61(m,2H),2.16(q,J＝7.2Hz,2H),1.76(s,1H),1.71–1.61(m,2H),1.49–1.39(m,2H).
催化实验5
催化生成：Z-5-(4’-硝基)苯氧基-2-戊烯-1-醇
氮气保护下，将29.0mg(0.15mmol)4-(4’-硝基)苯氧基-1-丁烯和26.4mg(0.30mmol)Z-1,4-丁烯二醇加入反应试管中。向其中加入1mL含有6.1mg(8μmol)催化剂Ia的THF溶液，在60℃下搅拌8h。反应完产物过硅胶柱(10％乙酸乙酯的石油醚溶液-40％乙酸乙酯的石油醚溶液)。
得到黄色油状液体24.7mg(产率73.7％)，Z/E为98:2。1HNMR(400MHz,CDCl3)δ8.30-8.12(m,2H),7.02-6.88(m,2H),5.90-5.75(m,1H),5.75-5.58(m,1H),4.27(d,J＝6.7Hz,2H),4.10(t,J＝6.4Hz,2H),2.65(q,J＝6.7Hz,2H),1.62(s,1H).
催化实验6
催化生成：Z-1,6-(4’-硝基)苯氧基-3-己烯
氮气保护下，将29.0mg(0.15mmol)4-(4’-硝基)苯氧基-1-丁烯加入反应试管中。向其中加入1mL含有6.1mg(8μmol)催化剂Ia的THF溶液，在60℃下搅拌8h。反应完产物过硅胶柱(10％二氯甲烷的石油醚溶液)。
得到深黄色油状液体15.4mg(产率57.2％)，Z/E为99：1。1H NMR(400MHz,CDCl3)δ8.22(d,J＝9.2Hz,2H),6.96(d,J＝9.2Hz,2H),5.69(t,J＝4.8Hz,2H),4.12(t,J＝6.5Hz,2H),2.67(dd,J＝12.0,6.3Hz,2H).
催化实验7
催化生成：Z-苯甲酸(12-羟基-10-烯)十二酯
氮气保护下，将34.8mg(0.127mmol)苯甲酸(10-烯)十一酯和22.4mg(0.254mmol)Z-1,4-丁烯二醇加入反应试管中。向其中加入1mL含有6.0mg(8μmol)催化剂Ib的THF溶液，在60℃下搅拌8h。反应完产物过硅胶柱(20％乙醚的石油醚溶液)。
得到深黄色油状液体24.7mg(产率64.0％)，Z/E为98:2。1HNMR(400MHz,CDCl3)δ＝8.05(d,J＝7.8,2H),7.55(t,J＝7.3,1H),7.44(t,J＝7.5,2H),5.66-5.56(m,1H),5.56-5.44(m,1H),4.31(t,J＝6.6,2H),4.19(t,J＝5.1,2H),2.06(dd,J＝13.7,6.8,2H),1.81-1.72(m,2H),1.54(s,1H),1.49–1.40(m,2H),1.35(s,4H),1.29(s,7H)；13C NMR(151MHz,CDCl3)δ133.23,132.84,130.50,129.55,128.34,65.15,58.63,29.72,29.59,29.46,29.39,29.25,29.18,28.71,27.43,26.02.
催化实验8
催化生成：Z-苯甲酸(7-羟基-5-烯)庚酯
氮气保护下，将25.9mg(0.127mmol)苯甲酸(5-烯)己酯和22.4mg(0.254mmol)Z-1,4-丁烯二醇加入反应试管中。向其中加入1mL含有6.0mg(8μmol)催化剂Ib的THF溶液，在60℃下搅拌8h。反应完产物过硅胶柱(20％乙醚的石油醚溶液)。
得到深黄色油状液体22.3mg(产率72.0％)，Z/E为99:1。1HNMR(400MHz,CDCl3)δ＝8.04(d,J＝7.8,2H),7.56(t,J＝7.3,1H),7.44(t,J＝7.5,2H),5.69-5.59(m,1H),5.53(dd,J＝18.0,7.5,1H),4.32(t,J＝6.6,2H),4.21(t,J＝5.8,2H),2.16(q,J＝7.3,2H),1.79(dt,J＝14.1,6.5,3H),1.58–1.45(m,2H).13C NMR(151MHz,CDCl3)δ166.72,132.93,132.32,130.36,129.56,129.06,128.38,64.76,58.57,28.21,26.95,25.93.
催化实验9
催化生成：Z-1,10-二邻苯甲酰亚胺基-5-癸烯
氮气保护下，将29.1mg(0.127mmol)1-邻苯二甲酰亚胺基-5-己烯加入反应试管中。向其中加入1mL含有6.0mg(8μmol)催化剂Ib的THF溶液，在60℃下搅拌8h。反应完产物过硅胶柱(10％乙醚的石油醚溶液)。
得到深黄色油状液体11.8mg(产率46.0％)，Z/E为98:2。1H NMR(600MHz,CDCl3)δ7.83(dd,J＝5.3,3.0,2H),7.70(dd,J＝5.4,3.0,2H),5.42-5.28(m,1H),3.72-3.59(m,2H),2.07(dd,J＝12.6,7.1,2H),1.97-1.40(m,4H),1.40-1.35(m,1H)；13C NMR(151MHz,CDCl3)δ168.48,133.86,132.16,130.21,129.66,123.18,37.91,32.07,28.13,26.86,26.71.
催化实验10
催化生成：Z-苯甲酸(5-癸烯)-1,10-二酯
氮气保护下，将25.9mg(0.127mmol)苯甲酸-5-己烯脂加入反应试管中。向其中加入1mL含有6.0mg(8μmol)催化剂Ib的THF溶液，在60℃下搅拌8h。反应完产物过硅胶柱(10％乙醚的石油醚溶液)。
得到深黄色油状液体12.1mg(产率50.0％)，Z/E为98:2。1H NMR(400MHz,CDCl3)δ8.08-7.99(m,2H),7.59-7.51(m,1H),7.43(t,J＝7.6,2H),5.43(ddd,J＝14.5,6.5,3.3,2H),4.32(t,J＝6.6,4H),2.16-2.01(m,4H),1.77(ddd,J＝9.6,6.8,3.3,4H),1.56-1.49(m,4H)；13C NMR(151MHz,CDCl3)δ132.87,130.39,129.81,129.55,128.35,64.96,28.35,28.21,26.85,26.13.
参考文献
(1)K.Endo,R.H.Grubbs,J.Am.Chem.Soc.,2011,133(22),8525
(2)B.K.Keitz,K.Endo,M.B.Herbert,R.H.Grubbs,J.Am.Chem.Soc.,2011,133(25),9686
(3)R.K.M.Khan,S.Torker,A.H.Hoveyda,J.Am.Chem.Soc.,2014,136,14337
(4)M.J.Koh,R.K.M.Khan,S.Torker,M.Yu,M.S.Mikus,A.H.Hoveyda,Nature,2015,517,181
(5)Adrian-Radu Popescu,Ana Daniela Musteti,Albert Ferrer-Ugalde,Clara
Figure BDA0001257909620000081
Rosario Nffl
Figure BDA0001257909620000082
Francesc Teixidor,Chem.-Eur.J.,2012,18(11),3174-3184.
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Claims (3)

1.Z-选择性钌烯烃复分解催化剂，其特征是用式(I)所示：
Figure FDA0002572007540000011
其中：Mes为2,4,6-三甲基苯基；X为氧或硫。
2.权利要求1的Z-选择性钌烯烃复分解催化剂的制备方法，其特征包括如下步骤：
氮气条件下，将Hoveyda-Grubbs II催化剂(II)与碳硼烷二巯基锌盐(III)或碳硼烷二巯基钠盐(IV)溶于干燥的有机溶剂中，室温下搅拌，抽干有机溶剂，加入二氯甲烷后离心，收集上层清液，干燥得化合物(Ia)，所述有机溶剂为四氢呋喃、二氯甲烷或甲苯；反应式为：
Figure FDA0002572007540000012
其中：
Figure FDA0002572007540000013
或：
氮气条件下，将Hoveyda-Grubbs II催化剂(II)与碳硼烷二羟基钠盐(V)溶于干燥的有机溶剂中，室温下搅拌，抽干有机溶剂，加入二氯甲烷后离心，收集上层清液，干燥得化合物(Ib)，所述有机溶剂为四氢呋喃、二氯甲烷或甲苯；反应式为：
Figure FDA0002572007540000021
其中：
Figure FDA0002572007540000022
3.权利要求1的Z-选择性钌烯烃复分解催化剂在催化烯烃复分解反应产生Z-式烯烃产物中的应用。
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