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 PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 32
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 2,4, 6-trimethylphenyl Chemical group 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052717 sulfur Chemical group 0.000 claims abstract description 3
- 239000011593 sulfur Chemical group 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- KEQKAMYELZXRRN-UHFFFAOYSA-L zinc;sulfanide Chemical class [SH-].[SH-].[Zn+2] KEQKAMYELZXRRN-UHFFFAOYSA-L 0.000 claims description 7
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
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- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 32
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- 239000007787 solid Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
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- 238000002474 experimental method Methods 0.000 description 10
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- 239000000203 mixture Substances 0.000 description 7
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
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- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
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- 238000001914 filtration Methods 0.000 description 3
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 2
- IORZJOJSTUVEQE-UHFFFAOYSA-N 2-hex-5-enylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCCCC=C)C(=O)C2=C1 IORZJOJSTUVEQE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NHZYQUOOLAYGLZ-UHFFFAOYSA-N but-1-enoxybenzene Chemical compound CCC=COC1=CC=CC=C1 NHZYQUOOLAYGLZ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- XVTCWUFLNLZPEJ-UHFFFAOYSA-N 1-(4-hydroxy-3-prop-2-enylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(O)C(CC=C)=C1 XVTCWUFLNLZPEJ-UHFFFAOYSA-N 0.000 description 1
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- MYBVZHQJQHJQOL-CLTKARDFSA-N 2-[(Z)-7-hydroxyhept-5-enyl]isoindole-1,3-dione Chemical compound c1cccc2c1C(=O)N(CCCC\C=C/CO)C2=O MYBVZHQJQHJQOL-CLTKARDFSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical class C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 1
- NKPBCHVQQSRKQE-UPHRSURJSA-N C(CCC\C=C/CCCCN1C(C2=CC=CC=C2C1=O)=O)N1C(C2=CC=CC=C2C1=O)=O Chemical compound C(CCC\C=C/CCCCN1C(C2=CC=CC=C2C1=O)=O)N1C(C2=CC=CC=C2C1=O)=O NKPBCHVQQSRKQE-UPHRSURJSA-N 0.000 description 1
- OWJDOEBSIZIZLY-IHWYPQMZSA-N CC(=O)c1ccc(O)c(C\C=C/CO)c1 Chemical compound CC(=O)c1ccc(O)c(C\C=C/CO)c1 OWJDOEBSIZIZLY-IHWYPQMZSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZKVZSBSZTMPBQR-UHFFFAOYSA-N Civetone Natural products O=C1CCCCCCCC=CCCCCCCC1 ZKVZSBSZTMPBQR-UHFFFAOYSA-N 0.000 description 1
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- JSOUQBYHODQLSS-UITAMQMPSA-N [(Z)-4-hydroxybut-1-enyl] benzoate Chemical compound C1=CC=C(C=C1)C(=O)O/C=C\CCO JSOUQBYHODQLSS-UITAMQMPSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZKVZSBSZTMPBQR-UPHRSURJSA-N civetone Chemical compound O=C1CCCCCCC\C=C/CCCCCCC1 ZKVZSBSZTMPBQR-UPHRSURJSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- PQIBBBNRBHLKLI-UHFFFAOYSA-N hex-5-enyl benzoate Chemical compound C=CCCCCOC(=O)C1=CC=CC=C1 PQIBBBNRBHLKLI-UHFFFAOYSA-N 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YEHGKFOTJWYCBN-UHFFFAOYSA-N undecyl benzoate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1 YEHGKFOTJWYCBN-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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Abstract
Description
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:
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:
其中:
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:
其中:
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。
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。
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。
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%)。
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,ClaraRosario Nffl Francesc Teixidor,Chem.-Eur.J.,2012,18(11),3174-3184.
(6)Keivan Sadrerafi,Ellen E.Moore,Mark W.Lee Jr.,J.Incl.Phenom.Macro.,2015,83(1),159-166。
Claims (3)
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:
其中:
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:
其中:
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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