CN113000066A - Z-selective ruthenium carbene olefin metathesis catalyst, and preparation method and application thereof - Google Patents
Z-selective ruthenium carbene olefin metathesis catalyst, and preparation method and application thereof Download PDFInfo
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- CN113000066A CN113000066A CN202110027181.7A CN202110027181A CN113000066A CN 113000066 A CN113000066 A CN 113000066A CN 202110027181 A CN202110027181 A CN 202110027181A CN 113000066 A CN113000066 A CN 113000066A
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- ruthenium carbene
- olefin metathesis
- carbene olefin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 30
- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 28
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- -1 ruthenium carbene olefins Chemical class 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000003446 ligand Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007704 transition Effects 0.000 abstract description 5
- 125000001246 bromo group Chemical group Br* 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 238000005649 metathesis reaction Methods 0.000 abstract description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract description 2
- WEHMXWJFCCNXHJ-UHFFFAOYSA-N propa-1,2-dienylbenzene Chemical compound C=C=CC1=CC=CC=C1 WEHMXWJFCCNXHJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 125000004434 sulfur atom Chemical group 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 84
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 64
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 239000003208 petroleum Substances 0.000 description 29
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000012230 colorless oil Substances 0.000 description 14
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- OZCRKDNRAAKDAN-IWQZZHSRSA-N (z)-but-1-ene-1,4-diol Chemical compound OCC\C=C/O OZCRKDNRAAKDAN-IWQZZHSRSA-N 0.000 description 10
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005686 cross metathesis reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical compound FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 description 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 2
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NXKFMUFJMLNJOB-UHFFFAOYSA-N [2-(hydroxymethyl)cyclopentyl]methanol Chemical compound OCC1CCCC1CO NXKFMUFJMLNJOB-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-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
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZKVZSBSZTMPBQR-UHFFFAOYSA-N Civetone Natural products O=C1CCCCCCCC=CCCCCCCC1 ZKVZSBSZTMPBQR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010082 LiAlH Inorganic materials 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- WRWAHQJHUIGGFL-RQOWECAXSA-N [N+](=O)([O-])C1=CC=C(OCCCC\C=C/CO)C=C1 Chemical compound [N+](=O)([O-])C1=CC=C(OCCCC\C=C/CO)C=C1 WRWAHQJHUIGGFL-RQOWECAXSA-N 0.000 description 1
- YGZFWGMKDUFODQ-UPHRSURJSA-N [N+](=O)([O-])C1=CC=C(OCC\C=C/CO)C=C1 Chemical compound [N+](=O)([O-])C1=CC=C(OCC\C=C/CO)C=C1 YGZFWGMKDUFODQ-UPHRSURJSA-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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- ZKVZSBSZTMPBQR-UPHRSURJSA-N civetone Chemical compound O=C1CCCCCCC\C=C/CCCCCCC1 ZKVZSBSZTMPBQR-UPHRSURJSA-N 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229940075931 sodium dithionate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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。
The invention discloses a Z-selective ruthenium carbene olefin metathesis catalyst. The catalyst utilizes the strong electron-withdrawing characteristics of bromine atoms to improve the reaction activity of the catalyst; the addition of bromine atoms also increases the steric hindrance of the whole ligand, improving the The selectivity of the catalyst is improved; the large steric hindrance makes the complex have a trigonal bipyramid coordination structure close to the intermediate transition state, which improves the catalytic activity of the catalyst. The catalyst also improves the stability and temperature resistance of the catalyst by inhibiting the nucleophilic addition reaction of the sulfur atom to the benzylidene carbene carbon. The invention also discloses a preparation method of the catalyst. The method has simple steps, mild reaction conditions, and the obtained catalyst has excellent thermal stability. The invention also discloses the application of the catalyst in catalyzing the metathesis reaction of ruthenium carbene olefins to prepare Z-form olefin products. The catalyst catalyzes the olefin reaction to obtain cis-form products with a specific configuration, and has high catalytic activity, high selectivity and product yield. high features.
Description
Technical Field
The invention belongs to the field of transition metal organic catalysts, and relates to a Z-selective ruthenium carbene olefin metathesis catalyst, and a preparation method and application thereof.
Background
The Z-type olefin has wide application in the fields of chemistry, biology, medicine and the like, and needs to be prepared by a rapid, efficient and stereoselective catalytic reaction, and the key of the catalytic reaction is a catalyst. Many natural open-chain compounds (e.g., oleic acid, linolenic acid), natural macrocyclic compounds (e.g., civetone, etc.), and some materials that are believed to have anti-cancer activity contain a Z-type olefin structure, but conventional olefin metathesis catalysts often yield a high proportion of E-type structural olefins in catalyzing the cross-metathesis (CM) of open-chain olefins and the metathesis (RCM) of closed-chain olefins that form macrocycles. Therefore, how to reshape the catalyst structure to obtain Z-type olefin structural product with high selectivity in the catalytic process is a hot spot in the research field of olefin metathesis nowadays.
Research in the field of olefin metathesis has resulted in breakthrough research efforts, but still faces significant difficulties and challenges. In 2011, a Z-selective ruthenium carbene olefin metathesis catalyst with chelated carboxyl is reported for the first time by Grubbs topic group, and the Z-type catalysis of cross metathesis is realized for the first time. However, the catalyst is unstable, low in catalytic activity and easy to decompose. Subsequent researches find that the catalytic activity and Z-selectivity of the catalyst are greatly improved after carboxyl in the catalyst is replaced by nitro, but the problem that the catalyst is easy to decompose is not solved yet. The Hoveyda group discovered in 2013 that when 1, 2-benzenedithiol was used as a ligand to replace two chlorine atoms in a compound, the resulting complex catalyzed ring-opening cross-metathesis of strained rings and yielded a product with a certain ratio of formula Z. The inventors found in 2019 that the catalyst exhibited excellent stability when 3, 4-dimercapto-1-cyclobutene-1, 2-dione was used instead of 2, 5-dichlorobenzenedimercapto, and could be stored for a long time even in the air. The 1, 8-naphthalene dimercapto chelated catalysts found in our subsequent studies have very high Z-selectivity, but lower catalytic activity.
From the above, the prior art has the following disadvantages: although some work has been done with the search for Z-selective olefin metathesis catalysts, it is still a general rule to find that it is possible to follow; there are fewer catalyst types, and the reported catalyst selectivity and activity are to be further improved. The nitro-chelated six-coordination Grubbs type catalyst has high catalytic activity and selectivity, but the synthesis process is complex, the stability is poor, and the applicability of functional groups is not high. The newly emerged ruthenium carbene catalyst containing the disulfide chelating ligand has simple synthetic process, better functional group applicability and huge application prospect. However, the activity and Z-selectivity of the bis-sulfur chelate ligand ruthenium carbene catalysts need to be further optimized.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the Z-selective ruthenium carbene olefin metathesis catalyst which has the characteristics of higher Z-type selectivity, better stability and higher catalytic efficiency in the ruthenium carbene olefin metathesis reaction.
The invention also aims to provide a preparation method of the Z-selective ruthenium carbene olefin metathesis catalyst.
The invention also aims to provide application of the Z-selective ruthenium carbene olefin metathesis catalyst in catalyzing ruthenium carbene olefin metathesis reaction to prepare Z-type olefin products.
One of the purposes of the invention is realized by adopting the following technical scheme:
a Z-selective ruthenium carbene olefin metathesis catalyst having the general structural formula i:
wherein Mes is 2,4, 6-trimethylphenyl.
The second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the Z-selective ruthenium carbene olefin metathesis catalyst comprises the following steps:
wherein:
dissolving Hoveyda catalyst (A) and 2,4,5, 7-tetrabromo-1, 8-dimercapto zinc salt (B) or 2,4,5, 7-tetrabromo-1, 8-sodium dithionate (C) in an organic solvent under the condition of nitrogen, stirring, drying in vacuum, adding dichloromethane, centrifuging, and removing the solvent to obtain a final product I, namely the 2,4,5, 7-tetrabromo-1, 8-naphthalene dirphobic ruthenium carbene compound.
Further, the organic solvent is tetrahydrofuran.
Further, the stirring temperature is 0 ℃ and the time is 0.5 h.
Preferably, the synthesis steps of compound B and compound C are:
reference is made to the synthesis of compounds 1-4: r.j.wright, c.lim, t.d.tilley, chem.eur.j.2009,15,8518.
Under the protection of nitrogen, compound 3(505.6mg, 1mmol) is dissolved in 20mL tetrahydrofuran, and LiAlH is slowly added at 0 DEG C4(114.0mg, 3mmol) for 1 h. After completion of the reaction, 1M HCl (10mL) was added, extracted with chloroform, dried over anhydrous sodium sulfate, and the solvent was removed to give compound 4(219.3mg,0.43 mmol).
Compound 4(507.6mg,1mmol), Zn (OAc)2·2H2O (876.9mg,4mmol,4.0equiv), ethylenediamine (0.40 mL,6mmol,6.00equiv.) were placed in a 25mL round bottom flask, 10mL isopropanol was added, and the mixture was stirred at room temperature for 2 h. The solid precipitate was filtered and washed with methanol (5mL for 3 times) and chloroform (5mL for 3 times), respectively. After suction drying, Compound B was obtained as a yellow solid (415.8mg, 0.73 mmol).
Compound 4(507.6mg,1mmol) and sodium tert-butoxide (107.9mg, 1.1equiv.) were dissolved in 10mL of methanol, stirred for 20min, spin dried, and washed with petroleum ether to give yellow compound C (518.5mg, 0.94 mmol).
The third purpose of the invention is realized by adopting the following technical scheme:
the application of the Z-selective ruthenium carbene olefin metathesis catalyst in catalyzing ruthenium carbene olefin metathesis reaction to prepare Z-type olefin products.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a Z-selective ruthenium carbene olefin metathesis catalyst, which utilizes the strong electron drawing characteristic of bromine atoms in 2,4,5, 7-tetrabromo-1, 8-naphthalene dirhobic groups to reduce the electron cloud density of a metal ruthenium center, so that the metal ruthenium center is more easily coordinated with olefin, the rate of generating a metal four-membered ring transition state is improved, and the reaction activity of the catalyst is further improved.
The catalyst provided by the invention improves the stability and temperature tolerance of the complex by inhibiting the nucleophilic addition reaction of sulfur atoms to benzylidene carbene carbon; meanwhile, the steric hindrance of the whole ligand can be increased by adding bromine atoms, so that the selectivity of the catalyst is improved.
The invention utilizes the large steric hindrance effect of the 2,4,5, 7-tetrabromo-1, 8-naphthalene dirichthynyl ligand to increase the repulsive force between the ligand and the N-heterocyclic carbene ligand, thereby forcing the ligand to be far away from the N-heterocyclic carbene ligand which also has large steric hindrance as much as possible, leading the complex to have a triangular bipyramidal coordination structure which is close to an intermediate transition state, and improving the catalytic activity of the catalyst; the large steric hindrance of the ligand can also make the transition state generated in the reaction process of the complex have a more compact spatial environment, thereby improving the three-dimensional control capability of the substituent group in the four-membered ring transition state.
2. The invention also provides a preparation method of the catalyst, the method has simple steps and mild reaction conditions, and the prepared product has excellent thermal stability.
3. The invention also provides application of the catalyst in catalyzing ruthenium carbene olefin metathesis reaction to prepare Z-type olefin products, and the catalyst can be used for catalyzing olefin reaction to obtain cis-type products with specific configurations, and has the characteristics of high catalytic activity, high Z-type selectivity and high product yield.
Drawings
FIG. 1 is a graph showing the results of the thermal stability test of the catalyst of the present invention.
Detailed Description
The present invention will be further described with reference to the following detailed description and the accompanying drawings, which are used for explaining the present invention, and the following embodiments or technical features may be arbitrarily combined to form new embodiments without conflict.
Example 1
A Z-selective ruthenium carbene olefin metathesis catalyst has a structural general formula I, and is prepared by the following steps: hoveyda catalyst A (187.5mg,2.4mmol) and 2,4,5, 7-tetrabromo-1, 8-dihydrocarbyl zinc salt B (236.0mg,0.4mmol) were dissolved in 5mL tetrahydrofuran under nitrogen in a 10mL round bottom flask, stirred at 0 ℃ for 0.5h, dried under vacuum after the reaction was complete, centrifuged after dichloromethane was added, and the solvent was removed to give final product I as a tan solid powder (196.4mg, 74.1% yield).
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.
Example 2
Example 2 differs from example 1 in that: the same procedures used in example 1 were repeated except for replacing 2,4,5, 7-tetrabromo-1, 8-dihydrocarbyl zinc salt (B) with sodium 2,4,5, 7-tetrabromo-1, 8-disulfo-nate (C) to give final product I (145.6mg, yield 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.
Experimental example 1
And (3) catalytic generation: ((Z) -2- ((1 ' S,3 ' R) -3 ' -vinylcyclopentyl) vinyl) benzene
14.3mg (0.15mmol) of norbornene and 312.3mg (3mmol) of styrene were introduced into a reaction tube under nitrogen, followed by addition of a solution of 4.8mg (4.5. mu. mol,3.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran), and stirring was carried out at room temperature for 4 hours. The reaction product was passed through a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to give 28.1mg (yield 95.0%) of a colorless oil with a Z/E of 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.
Experimental example 2
And (3) catalytic generation: (Z) -1-fluoro-4- (2- ((1 ' S,3 ' R)3 ' -vinylcyclopentyl) vinyl) benzene
14.3mg (0.15mmol) of norbornene and 366.2mg (3mmol) of 4-fluorostyrene were introduced into a reaction tube under nitrogen, followed by addition of a solution of 4.8mg (4.5. mu. mol,3.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran), and stirring was carried out at room temperature for 4 hours. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to obtain 30.2mg (yield 93.0%) of a colorless oil having a Z/E ratio of 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.
Experimental example 3
And (3) catalytic generation: (3- (Z) -styryl-5-vinyl) cyclopentane-1, 2-dimethanol
Under a nitrogen atmosphere, 23.1mg (0.15mmol) of norbornene dimethanol and 312.3mg (3mmol) of styrene were charged into a reaction tube, followed by addition of a solution of 4.8mg (4.5. mu. mol,3.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran), and stirring was carried out at room temperature for 4 hours. The reaction product was passed through a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to give 34.5mg (yield 89%) of a colorless oil with a Z/E of 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.
Experimental example 4
And (3) catalytic generation: (3- (Z) -4-fluorostyryl-5-vinyl) cyclopentane-1, 2-dimethanol
Under a nitrogen atmosphere, 23.1mg (0.15mmol) of norbornene dimethanol and 366.2mg (3mmol) of 4-fluorostyrene were added to a reaction tube, followed by addition of a solution of 4.8mg (4.5. mu. mol,3.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran), and stirring was carried out at room temperature for 4 hours. The reaction product was passed through a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to give 38.9mg (yield 94%) of a colorless oil with a Z/E of 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.
Experimental example 5
And (3) catalytic generation: (Z) -4-hydroxy-2-butene-1-benzoic acid ester
19.4mg (0.12mmol) of allyl benzoate and 22.4mg (0.24mmol) of Z-butene-1, 4-diol under nitrogen were added to a solution of 6.4mg (6.0. mu. mol,5.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran) and stirred at 60 ℃ for 6 h. The reaction product was passed through a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to give 18.1mg (yield 78.7%) of a colorless oil with a Z/E of 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.
Experimental example 6
And (3) catalytic generation: (Z) -7-hydroxy-5-heptene-1-benzoic acid ester
24.5mg (0.12mmol) of allyl benzoate and 22.4mg (0.24mmol) of Z-butene-1, 4-diol under nitrogen were added to a solution of 6.4mg (6.0. mu. mol,5.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran) and stirred at 60 ℃ for 6 h. After the reaction, the product was applied to a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to obtain 23.6mg (yield: 84.0%) of a colorless oil having a Z/E ratio of 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.
Experimental example 7
And (3) catalytic generation: (Z) -12-hydroxy-10-dodecene-1-benzoate
32.9mg (0.12mmol) of allyl benzoate and 22.4mg (0.24mmol) of Z-butene-1, 4-diol under nitrogen, are added to a solution of 6.4mg (6.0. mu. mol,5.0 mol%) of the catalyst from example 1 in 1mL of THF (tetrahydrofuran) and stirred at 60 ℃ for 6 h. After the reaction, the product was passed through a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to obtain 30.3mg (yield: 84.0%) of a colorless oil having a Z/E ratio of 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.
Experimental example 8
And (3) catalytic generation: (Z) -5- (4' -nitrophenoxy) -2-penten-1-ol
23.1mg (0.12mmol) of allyl benzoate and 22.4mg (0.24mmol) of Z-butene-1, 4-diol under nitrogen, followed by addition of a solution of 6.4mg (6.0. mu. mol,5.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran), stirring at 60 ℃ for 6 h. After the reaction, the product was applied to a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to obtain 21.7mg (yield: 81.2%) of a colorless oil having a Z/E ratio of 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.
Experimental example 9
And (3) catalytic generation: (Z) -7- (4' -nitrophenoxy) -2-hepten-1-ol
26.5mg (0.12mmol) of allyl benzoate and 22.4mg (0.24mmol) of Z-butene-1, 4-diol under nitrogen, followed by addition of a solution of 6.4mg (6.0. mu. mol,5.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran), stirring at 60 ℃ for 6 h. After the reaction, the product was applied to a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to obtain 26.2mg (yield 86.9%) of a colorless oil having a Z/E ratio of 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.
Experimental example 10
And (3) catalytic generation: (Z) -2- (5 '-hydroxy-3' -pentenyl) -isoindoline-1, 3-dione
24.1mg (0.12mmol) of allyl benzoate and 22.4mg (0.24mmol) of Z-butene-1, 4-diol are added under nitrogen, followed by addition of 6.4mg (6.0. mu. mol,5.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran), and stirring is carried out at 60 ℃ for 6 h. The reaction product was passed through a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to give 23.2mg (yield 83.5%) of a colorless oil with a Z/E of 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.
Experimental example 11
And (3) catalytic generation: (Z) -2- (7 '-hydroxy-5' -heptenyl) -isoindoline-1, 3-dione
Under nitrogen, 27.5mg (0.12mmol) of allyl benzoate and 22.4mg (0.24mmol) of Z-butene-1, 4-diol were added, followed by addition of 6.4mg (6.0. mu. mol,5.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran), and stirring was carried out at 60 ℃ for 6 hours. After the reaction, the product was applied to a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to obtain 27.9mg (yield 89.6%) of a colorless oil having a Z/E ratio of 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＝7.4,1.5 Hz,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.
Experimental example 12
And (3) catalytic generation: (Z) -4- (7 ' -hydroxy-5 ' -hepten-1 ' -yloxy) benzaldehyde
24.1mg (0.12mmol) of allyl benzoate and 22.4mg (0.24mmol) of Z-butene-1, 4-diol are added under nitrogen, followed by addition of 6.4mg (6.0. mu. mol,5.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran), and stirring is carried out at 60 ℃ for 6 h. The reaction product was passed through a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to give 24.3mg (yield 86.4%) of a colorless oil with a Z/E of 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.
Experimental example 13
And (3) catalytic generation: 4- [ (3 'Z) -5' -hydroxy-3 '-penten-1' -yloxy ] benzoic acid methyl ester
24.7mg (0.12mmol) of allyl benzoate and 22.4mg (0.24mmol) of Z-butene-1, 4-diol under nitrogen were added to a solution of 6.4mg (6.0. mu. mol,5.0 mol%) of the catalyst obtained in example 1 in 1mL of THF (tetrahydrofuran) and stirred at 60 ℃ for 6 h. The reaction product was passed through a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to give 24.0mg (yield 84.7%) of a colorless oil with a Z/E of 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.
Experimental example 14
And (3) catalytic generation: 4- [ (5 ' Z) -7 ' -hydroxy-3 ' -hepten-1-yloxy ] benzoic acid methyl ester
28.1mg (0.12mmol) of allyl benzoate and 22.4mg (0.24mmol) of Z-butene-1, 4-diol under nitrogen, are added to a solution of 6.4mg (6.0. mu. mol,5.0 mol%) of the catalyst from example 1 in 1mL of THF (tetrahydrofuran) and stirred at 60 ℃ for 6 h. The reaction product was passed through a silica gel column (10% ethyl acetate in petroleum ether-60% ethyl acetate in petroleum ether) to give 24.5mg (yield 77.4%) of a colorless oil with a Z/E of 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).13C NMR(101 MHz,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.
Experimental example 15
Catalyst thermal stability test
The catalyst I obtained by the invention and the catalysts D and E reported by the inventor before are subjected to thermal stability test under the same conditions, namely anthracene is taken as an internal standard and used at 55 DEG C1H NMR monitored the decomposition of catalyst I, D, E in THF-d 8. Wherein the structural formulas of the catalysts D and E are respectively as follows:
9.8mg of each of the catalysts D, E and I was placed in a nuclear magnetic tube, 3.6mg (0.02mmol) of the internal standard anthracene was added, and 0.5mL of anhydrous deuterated tetrahydrofuran (THF-d8) was added to the nuclear magnetic tube. The hydrogen spectra of the three catalysts were tested continuously in a brook nuclear magnetic instrument every 30min at a temperature of 55 ℃. The rate of decomposition of the catalyst was determined by monitoring the peak areas of the hydrogen atoms on the carbene carbon and of the internal standard.
The results are shown in FIG. 1: the catalyst I obtained by the invention has the slowest decomposition rate relative to the catalyst D, E, which shows that the thermal stability of the catalyst I obtained by the invention is greatly improved.
In conclusion, the Z/E ratio of the product obtained by the 2,4,5, 7-tetrabromo-1, 8-naphthalene dirichiphenyl ruthenium carbene catalyst in the catalytic olefin metathesis reaction is as high as 99:1, the yield is as high as 95%, and the catalyst has the characteristics of good stability, high reaction activity, strong Z-type selectivity and high yield. Overcomes the defects of low catalyst activity, poor Z-selectivity and the like in the research on Z-selective olefin double decomposition catalysis in the prior art, and has good application prospect.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (5)
1. A Z-selective ruthenium carbene olefin metathesis catalyst, having the general structural formula i:
wherein Mes is 2,4, 6-trimethylphenyl.
2. The method of preparing a Z-selective ruthenium carbene olefin metathesis catalyst of claim 1, comprising the steps of:
wherein:
under the condition of nitrogen, dissolving Hoveyda catalyst (A) and 2,4,5, 7-tetrabromo-1, 8-dimercapto zinc salt (B) or 2,4,5, 7-tetrabromo-1, 8-sodium dithioate (C) in an organic solvent, stirring, drying in vacuum, adding dichloromethane, centrifuging, and removing the solvent to obtain a final product I.
3. The method of preparing a Z-selective ruthenium carbene olefin metathesis catalyst of claim 2, wherein the organic solvent is tetrahydrofuran.
4. The method of preparing a Z-selective ruthenium carbene olefin metathesis catalyst of claim 2, wherein the stirring temperature is 0 ℃ for 0.5 h.
5. The use of a Z-selective ruthenium carbene olefin metathesis catalyst of claim 1 to catalyze a ruthenium carbene olefin metathesis reaction to produce a Z-type olefin product.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070282148A1 (en) * | 2005-12-16 | 2007-12-06 | Jacob Berlin | Organometallic ruthenium complexes and related methods for the preparation of tetra-substituted and other hindered olefins |
| US20090156766A1 (en) * | 2007-09-20 | 2009-06-18 | Lemcoff Gabriel N | Sulfur chelated ruthenium compounds useful as olefin metathesis catalysts |
| WO2011059803A2 (en) * | 2009-10-29 | 2011-05-19 | Board Of Regents, The University Of Texas System | Ruthenium-alkylidenes containing acyclic diaminocarbenes for obtaining low e/z ratios in cross metathesis |
| CN106939026A (en) * | 2017-03-09 | 2017-07-11 | 上海克琴科技有限公司 | A kind of preparation and its application of ruthenium metal olefin metathesis catalyst |
| CN109225334A (en) * | 2018-07-20 | 2019-01-18 | 吉林化工学院 | A kind of ruthenium olefin metathesis catalyst and its preparation method and application with ortho position steric hindrance structure |
| CN109794292A (en) * | 2019-01-10 | 2019-05-24 | 天津大学 | Z-selective ruthenium carbene olefin metathesis catalyst and its preparation method and application |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070282148A1 (en) * | 2005-12-16 | 2007-12-06 | Jacob Berlin | Organometallic ruthenium complexes and related methods for the preparation of tetra-substituted and other hindered olefins |
| US20090156766A1 (en) * | 2007-09-20 | 2009-06-18 | Lemcoff Gabriel N | Sulfur chelated ruthenium compounds useful as olefin metathesis catalysts |
| WO2011059803A2 (en) * | 2009-10-29 | 2011-05-19 | Board Of Regents, The University Of Texas System | Ruthenium-alkylidenes containing acyclic diaminocarbenes for obtaining low e/z ratios in cross metathesis |
| CN106939026A (en) * | 2017-03-09 | 2017-07-11 | 上海克琴科技有限公司 | A kind of preparation and its application of ruthenium metal olefin metathesis catalyst |
| CN109225334A (en) * | 2018-07-20 | 2019-01-18 | 吉林化工学院 | A kind of ruthenium olefin metathesis catalyst and its preparation method and application with ortho position steric hindrance structure |
| CN109794292A (en) * | 2019-01-10 | 2019-05-24 | 天津大学 | Z-selective ruthenium carbene olefin metathesis catalyst and its preparation method and application |
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