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WO2007017047A1 - Complexes carbene-metal n-heterocycliques immobilisables comportant des groupes alcoxysilyle - Google Patents

Complexes carbene-metal n-heterocycliques immobilisables comportant des groupes alcoxysilyle Download PDF

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WO2007017047A1
WO2007017047A1 PCT/EP2006/006987 EP2006006987W WO2007017047A1 WO 2007017047 A1 WO2007017047 A1 WO 2007017047A1 EP 2006006987 W EP2006006987 W EP 2006006987W WO 2007017047 A1 WO2007017047 A1 WO 2007017047A1
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heteroatom
hydrocarbon
carbon atoms
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Katrin Koehler
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Merck Patent GmbH
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Merck Patent GmbH
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    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • 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
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support

Definitions

  • the invention relates to novel immobilizable N-heterocyclic carbene metal complexes and their analogs immobilized on inorganic carriers.
  • the invention further relates to the use of the novel compounds as catalysts in organic, organometallic and transition metal catalyzed reactions.
  • N-heterocyclic carbene-metal complexes of the type A and B are described, for example, in the reviews Angew. Chem. 1997, 109, 2256-2282; Angew. Chem. 2002, 114, 1342-1363; Tetrahedron: Asymmetry 2003, 14, 951-961 and Coordination Chemistry Reviews 2004, 248, 2247-2273.
  • N-heterocyclic carbenes type C and D
  • metal complexes occurs either by ligand exchange reactions on metal-complex compounds or by association reactions on metal compounds.
  • N-heterocyclic carbene complexes of type A and B have in recent years as efficient catalysts in the most diverse Chem., 2002, 114, 1342-1363; Tetrahedron: Asymmetry 2003, 14, 951-961; Chemtracts - Organic Chemistry, 2003, 205-227; Coordination Chemistry Reviews 2004, 248, 2239-2246). They are used as homogeneous catalysts. The separation of these homogeneous
  • the immobilization of homogeneous catalysts can be carried out on organic polymers, such as polystyrene, or on inorganic oxides, such as silica gel.
  • Organic support materials have many disadvantages compared to the very robust inorganic support materials: mechanical instability and heavy swelling depending on the solvents used, which can lead to diffusion problems and thus to reduced catalyst activities in the application reactions.
  • Inorganic oxides such as silica gel have high thermal stability compared to the organic carriers and are commercially available in a wide range of porosity and specific surface area. They can be functionalized in simple chemical reactions via the silanol groups of the silica gel (Journal of Chromatography A 1990, 343-355, Colloids and Surfaces A: Physiochemical and Engineering Aspects 1995, 98, 235-241, Journal of SoI-GeI Science and Technology 1997 ', 8, 173-176. Trialkoxysilyl functions are very well suited for immobilization of molecules on inorganic oxides, since the immobilization process is very simple and proceeds under mild conditions. As a by-product, only the corresponding alcohol is formed in the reaction of (RO) 3 Si functions with the OH groups of the inorganic oxides
  • the molecule to be immobilized is firmly bound to the support via covalent Si-O bonds.
  • the by-product formed is HCl, which must be neutralized by addition of the base.
  • the resulting by-product must also be separated by complex methods.
  • the binding of the molecules to the carrier can also be effected via ionic interaction. However, it comes in subsequent reactions, depending on the solvent used to detach the molecules from the carrier, the so-called catalyst leaching.
  • the alkoxysilyl group must not be bound in the immediate vicinity of the catalytically active metal center. It should generally have a certain distance to the molecule center. A sufficient distance is necessary so that the molecule still has some flexibility in translational and rotational movements even after immobilization on a support. This distance can be ensured by a linker of sufficient length.
  • the object of the present invention is therefore to provide suitable immobilizable N-heterocyclic carbenes or N-heterocyclic carbene-metal complexes with improved molecular stability and reduced tendency to dimerizations, which are in the form of metal-carbene complexes for use as catalysts and during the reactions lead to high activities, productivity and selectivities, where they have a long life. It is also an object of the present invention to provide a simple and inexpensive process for the preparation of these compounds.
  • the object of the present invention is therefore in particular to make immobilisable N-heterocyclic carbenes or N-heterocyclic carbene-metal complexes with improved properties available.
  • Another object of the invention is to covalently immobilize these novel compounds with improved properties on inorganic oxides so that they are available in sufficient quantity on the support surface for application reactions. They should be firmly anchored on the surface and show no leaching. These new substances should be produced in a simple manner and have a sufficiently high thermal stability. In addition, they should show good, preferably improved, efficiency as catalysts in corresponding application reactions. 2. Description of the invention
  • N-heterocyclic carbenes which are substituted in the 4- or 5-position of the heterocycle by alkoxysilyl groups 5 (types E and F), have these improved properties. From the
  • N-heterocyclic carbene-metal complexes with alkoxysilyl functions accessible via the backbone i. H. can be bonded to inorganic oxides via the 4- or 5- position of the heterocycle
  • R1, R3, R4, R5, R6 independently
  • H Hal, unbranched or branched hydrocarbon having up to 30 carbon atoms, substituted unbranched or branched hydrocarbon having up to 30 carbon atoms, heteroatom-containing hydrocarbon having up to 30 carbon atoms, wherein the heteroatom N, S or O be may be, substituted heteroatom-containing hydrocarbon having up to 30 carbon atoms, wherein the heteroatom N, S or O may be and wherein the hydrocarbon chain may be substituted by F or an N, S or O-containing group, respectively
  • Carrier inorganic oxide, with active OH groups on the surface mean Carrier inorganic oxide, with active OH groups on the surface mean.
  • the present invention also relates to the use of
  • these compounds are used as catalysts in the olefin
  • novel compounds of the general formulas (I) and (II) can be immobilized covalently on inorganic carriers to form the compounds of the general formula (Ia) and (IIa).
  • the compounds Ia-Ha can also be built up stepwise on the support in a solid-phase synthesis from suitable precursors.
  • the immobilization takes place by reaction of the compounds I and II with an inorganic metal oxide in anhydrous, inert, aprotic organic solvents.
  • the reaction produces as by-product an alcohol R'OH.
  • the products Ia and IIa can advantageously be separated by filtration from the solvent and ROH. You can optionally further purified by washing with a suitable solvent, if necessary.
  • the immobilization can be carried out both in a batch process and continuously. If the preparation of Ia and IIa in a solid phase synthesis stepwise on the support, the connection of the molecules takes place on the inorganic support via linker building blocks.
  • the compounds of the general formula (I) can be used as starting materials for the preparation of the compounds of the general formula (Ia) and the compounds (II) can be used as starting materials for the preparation of (IIa).
  • the compounds of the general formulas (I), (II), (Ia) and (IIa) are outstandingly suitable as immobilisable or immobilized catalysts or as components in organic and organometallic synthesis.
  • they can be used as catalysts in hydrogenation, carbonylation, amination, allylation, oxidation, reduction, coupling (Heck, Suzuki, Stille, Sonogashira Negishi, Ullmann), olefin dimerization, olefin oligomerization, olefin telomerization, olefin polymerization and olefin metathesis be used.
  • immobilizable compounds (I) and (II) are that, in contrast to known compounds, they can be immobilized on inorganic oxides via the so-called backbone of the imidazole ring in the 4- or 5-position.
  • Compounds of this group show higher catalyst efficiencies in the application reactions, ie they become, compared to known compounds by the connection of the SiR ' n (OR') 3 -n group via the 4- or 5-position in (I) and (II) higher activities, productivities and selectivities found. Also, these types of catalysts each have a long life.
  • the conversions can be increased up to 55% compared to those known in the art.
  • the use of not bound to a support new catalysts leads to less expensive application methods.
  • By linking via a SiR'n (OR ') 3-n group to the 4- or 5-position of the catalyst molecule instead of the previously known binding in the 1- or 3-position of the imidazole ring can now be the 1- and 3 Position of the heterocyclic compound are substituted with arbitrarily large residues. The latter then take over the necessary neighborly stabilization and shielding of the carbene carbon atom in the 2-position of the heterocycle. In this way, increased steric and electronic stabilization of the carbene function is given.
  • compounds (I) and (II) according to the invention Due to their molecular structure, compounds (I) and (II) according to the invention have various advantages in comparison with corresponding known heterocyclic compounds: they can be immobilized on a support and have an increased molecular stability.
  • the increased stability is advantageously associated with a constant or even improved reactivity of the N-heterocyclic carbene metal complexes. It is of particular advantage that the compounds of general formulas (I) and (II) are thermally stable and accessible in simple syntheses.
  • the immobilized compounds (Ia) and (IIa) compared with the prior art are: Since the compounds of the general formulas (Ia) and (IIa) via the backbone of the imidazole ring in the 4- or 5-position to inorganic oxides As carriers are immobilized, they have high catalyst efficiencies in the application reactions, such as high activities, productivities and selectivities and in each case an increased lifetime. This, as well as in the carrier-free connections, the 1- and 3-
  • the immobilization is also in the application in catalytic reactions of great advantage, since the immobilized catalysts by filtration very easily separated from the reaction solutions or reaction products are. This can save considerable costs in all application reactions. In particular, this is the case in the separation and purification of the end products.
  • the compounds of the general formulas Ia and IIa can be easily recycled by the immobilization and used again in application reactions. This is of particular use since the very expensive compounds according to the invention can be used several times. As a result, the immobilization of I and II in all their applications leads to significant process cost savings, especially in catalytic reactions using expensive transition metal catalysts.
  • compounds of formula (I) is a 4,5-unsaturated dinitrogen heterocycle and in which of formula (II) before a saturated dinitrogen heterocycle.
  • substituents are attached to the two nitrogen atoms of the heterocycle and the carbon atom in the 2-position of the heterocycle, ie between the two nitrogen atoms, is located as a carbene carbon atom with a free one
  • Electron pair which is optionally coordinated to a metal complex fragment ML m .
  • the bond can be complex or covalent.
  • Compounds of the invention of the general formulas (Ia) and (IIa) differ from the compounds of the formulas (I) and (II) only in that instead of the SiR'n (OR ') n . 3 group is an inorganic support via the linker Z to the 4- or 5-position of the heterocycle bound.
  • the radicals R.sup.1, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 independently of one another preferably denote hydrocarbon radicals each having up to 30 carbon atoms.
  • R1 and R3 independently large, sterically demanding hydrocarbon radicals, such as. T-butyl, i-propyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, mesityl, cyclohexyl, adamantyl or like radicals.
  • R 4, R 5 and R 6 preferably each denote hydrogen, halogen or a hydrocarbon radical having up to 10 C atoms from the series of unbranched or branched alkyl radicals or substituted or unsubstituted aryl radicals.
  • R ' is again preferably a hydrocarbon radical having up to 10 C atoms.
  • R ' is an unbranched or branched alkyl radical having up to 10 C atoms.
  • the linker Z is preferably a hydrocarbon bridge having up to 30 carbon atoms.
  • Z may be a substituted hydrocarbon bridge having up to 30 carbon atoms, a substituted or unsubstituted heteroatom-containing hydrocarbon bridge having up to 30 carbon atoms.
  • Z is particularly preferably a hydrocarbon bridge which contains one or more functional group (s) as bridge member (s) or as substituent (s).
  • the functional group may each be an ester, thioester, anhydride, amide, keto, carbodiimide, carbamate, ether, acetal, thioether, disulfide, amine, imine or silyl group.
  • Z is particularly preferably a corresponding hydrocarbon bridge having up to 10 C atoms with the said functional groups.
  • a group ML m may be complexed or covalently bonded.
  • This group may be any metal complex fragment wherein M represents a metal atom, preferably a transition metal atom.
  • L is a suitable ligand.
  • M is an integer in the range of 1 to 5.
  • M may have the meaning of a metal atom from the group of transition metal atoms of groups IV to VIII of the Periodic Table of the Elements, but may also assume the meaning of Cu and Ag.
  • M is particularly preferably a transition metal atom selected from the group consisting of Ti, Zr 1 V, Nb, Ta, Cr, Mo, W, Mn, Re, Tc, Fe 1 Ru, Os, Co, Rh, Ir, Ni,
  • L can assume different meanings. Depending on the valency and nature of the metal atom, several ligands L may be present in the complex fragment. These in turn may be both anionic and neutral independently.
  • Anionic ligands are preferably Hal, selected from the group of halides Br “ , Cl “ , J “ and F " , or from the group of pseudohalides cyanide (CN “ ) and thiocyanate (SCN “ ).
  • L may also be a ligand selected from the group of pseudohalides cyanide (CN ' ) and thiocyanate (SCN “ ) and from the group chlorate (CIOs ' ) perchlorate (CIO 4 " ), hydride, hydroxyl, a carboxylic acid anion such.
  • Trifluoromethanesulfonaf tosylate “ (CH 3 C 6 H 4 SO 3 " ), nitrate “ (NO 3 “ ), nitrite “ (NO 2 " ), phosphorus hexafluoride (PF 6 “ ), antimony hexafluoride (SbF 6 “ ), boron tetrafluoride (BF 4 “ ) and boron tetrachloride (BCI 4 " ).
  • Preference is given to neutral ligands selected from the group CO, PR 3 (R alkyl, cycloalkyl, aryl), P (OR) 3 , N-heterocyclic carbene, cyclic N donor, such as pyridine, 2,2'-bipyridine or the like, Nitriles, isonitriles, olefins (COD), carbenes and the chelating carbenes with O, N or P donors.
  • N-heterocyclic carbene such as pyridine, 2,2'-bipyridine or the like
  • Nitriles, isonitriles, olefins (COD), carbenes and the chelating carbenes with O, N or P donors such as pyridine, 2,2'-bipyridine or the like.
  • the support may be inorganic oxides containing active OH groups on the surface. As a result, they are capable of reacting with the starting compounds of the general formulas (I) and (II) according to the invention.
  • inorganic oxides can be natural or chemical produced particulate or monolithic oxides of silicon, boron, aluminum, titanium and zirconium or corresponding oxide mixtures or their mixed oxides. Particular preference is given to using particulate or monolithic oxides of silicon, aluminum or their mixed oxides or zeolites. Particular preference is given to using particulate or monolithic oxides of silicon.
  • the silicon-containing materials can be silica gels or naturally occurring silicates, which are derived from chain, strip and layered silicas.
  • the compounds of the general formulas (I) and (II) according to the invention can be obtained by methods known to those skilled in the art for the preparation of N-heterocyclic carbene ligands and N-heterocyclic carbene metal complexes. Suitable methods of preparation are described for example in Tetrahedron 1999, 55, 14523-14534 or in Chem. Eur. J. 1996, 2, 772-780. In this case, imidazolium salts can be reacted with suitable deprotonation reagents to form the N-heterocyclic carbenes.
  • the latter can be converted into the N-heterocyclic carbene-metal complexes in association reactions with metal salts or in ligand-exchange reactions with metal-complex compounds. In some cases, even the synthesis of the N-heterocyclic carbene-metal complexes is possible directly from the imidazolium salts and the corresponding metal salts.
  • a suitable catalyst is needed for this reaction.
  • aprotic bases such as. B. tertiary
  • Amines from the series triethylamine, 1, 4-diazabicyclooctane, 1, 4-dimethylpiperazine, N-alkylmorpholines and 1, 2-dimethylimidazole or pyridine are used. It may also be suitable Lewis acids. Examples of these are BF 3 Et 2 O, Cu (halide), Zn (halide) 2 and Sm (halide) 2 or organotin compounds such as tributyltin acetate, dibutyltin diacetate, dibutyltin dilaurate, dimethyltin dichloride, or trimethyltin hydroxide.
  • various catalysts can also be used together. In experiments, the use of a combination of SmI 2 with 1, 3-dimethyltetrahydro-2 (1 H) pyrimidinone has been found to be particularly advantageous.
  • solvent aprotic solvents such as. B. cyclic ethers, in particular dioxane, and tetrahydrofuran, or dimethylformamide, dimethyl sulfoxide or halogenated hydrocarbons, such as CH 2 Cl 2 , chlorobenzene or the like can be used.
  • cyclic ethers in particular dioxane, and tetrahydrofuran, or dimethylformamide
  • dimethyl sulfoxide or halogenated hydrocarbons such as CH 2 Cl 2 , chlorobenzene or the like
  • halogenated hydrocarbons such as CH 2 Cl 2 , chlorobenzene or the like
  • the solvents can be used pure or in a mixture.
  • the reaction time varies depending on the educts used. It can be 30 minutes to 7 days. Usually, however, the reactions are completed within one hour to four days.
  • the product formed can be separated from the reaction mixture by simple filtration. Further purification can then be carried out by several washing processes.
  • the new compounds are the general ones
  • Formulas (I) and (II) can be used very well as catalysts for various reactions. Their use as catalysts in the Olefin metathesis studied in more detail. For example, selected representatives of these compounds have been used as catalysts in the cyclization olefin metathesis reaction (RCM) and the results achieved compared to those achieved using commonly used catalysts.
  • RCM cyclization olefin metathesis reaction
  • the immobilization of the compounds of the general formulas (I) and (II) takes place by reaction of the compounds (I) and (II) with an inorganic metal oxide in anhydrous, inert, aprotic organic solvents.
  • the order of addition of the components can be arbitrarily selected.
  • the starting compounds can be pre-dissolved or suspended in a suitable solvent.
  • pentane hexane, heptane, octane, decane, benzene or toluene are preferably used, most preferably heptane and toluene.
  • ethers tetrahydrofuran, diethyl ether or methyl tert-butyl ether are preferred. Under certain conditions, mixtures of these solvents can be used.
  • Nitrogen and argon in particular, have proven to be particularly suitable protective gases.
  • the starting compounds (I) and (II) are in a 0.01 to 100-fold stoichiometric excess with respect to the active OH groups on the
  • the reaction may be in a temperature range of -20 0 C to 150 0 C, preferably in the range from 0 0 C to +120 0 C, take place.
  • the reaction time is 30 minutes to 10 days, preferably 1 hour to 2 days, and more preferably 1 hour to 1 day.
  • the products (Ia) and (IIa) can be separated by filtration and can optionally be purified by washing with the abovementioned solvents and then dried.
  • the immobilization can be carried out both in a batch process and continuously. In the continuous process, the solutions of the compounds (I) and (II) described above by a z. B.
  • monolithic carrier material is pumped, wherein the monolith is heated to the appropriate reaction temperature.
  • the solutions of (I) and (II) can optionally be circulated and thus flow through the monolith several times. Here, the flow rates can be chosen arbitrarily. Subsequently, the functionalized monolith is washed with suitable solvents and used in the desired application reactions.
  • the support may be a commercially available SiO 2 to which corresponding compounds are covalently bonded via silyl groups.
  • Chlorosilanes (R ' 3 SiCI) or alkoxysilanes [R' 3 SiOR ', R' 2 Si (OR ') 2, R'Si (OR') 3 ] done.
  • This has the advantage that all accessible reactive OH functions on the carrier surface are converted into chemically inert groups, so that any decomposition reactions which may occur in subsequent reactions can no longer occur due to free OH functions with sensitive substrates.
  • N, N-diallyl-4-toluenesulfonamide F is used freshly distilled
  • silica gel 60 surface area 500 m 2 / g
  • 50 mg (0.076 mmol) of 2 are added.
  • the reaction solution is stirred under exclusion of light for 7 days at room temperature.
  • the functionalized silica gel is filtered off, washed with about 20 ml of dichloromethane and dried under high vacuum. 7 is obtained as a pale beige powder.
  • Loading [mmol / g] C 0.50, N 0.39.
  • IR (DRIFT): v 3610 (sh), 3354 (br), 2981 (w), 2930 (m), 1989 (br), 1870 (br), 1719 (m), 1629 (m), 1611 (sh ), 1521 (sh), 1489 (m), 1463 (w), 1413 (w), 1380 (W), 1287 (vs), 1233 (vs), 1068 (sh), 963 (sh), 815 cm ' 1 (m).
  • the N, N-diallyl-4-toluenesulfonamide F is used in freshly distilled (bulb-tube, 4.2 * 10 "1 mbar, 300 0 C).
  • the metathesis reaction is in a Carousel Reaction Station by Discovery Technologies performed. Is In the Carousel Reaction Tubes A 0.05 M substrate solution was prepared from 74.3 mg (0.3 mmol) F and 5.9 ml CH 2 Cb The tubes are placed in the carousel, purged with argon with the cock open and refluxed for 30 min, then 2.22 mg 8 (corresponding to 0.045 ⁇ mol The reaction solutions thus obtained are boiled for a period of 70 hours at 45 ° C. with a closed tap.
  • the analysis of the conversions of G takes place from time to time by means of HPLC, for which 4 drops are taken from each "reaction tube” and diluted with 900 .mu.l of methanol and measured.
  • reaction solution contained 7.8 ⁇ g of ruthenium, which corresponds to a ruthenium leaching of 3%.

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Abstract

L'invention concerne de nouveaux complexes carbène-métal N-hétérocycliques immobilisables, ainsi que leurs analogues immobilisés sur des supports inorganiques. Cette invention se rapporte en outre à l'utilisation de ces nouveaux composés en tant que réactifs de réactions organiques, de réactions organométalliques, et de réactions catalysées par des métaux de transition.
PCT/EP2006/006987 2005-08-09 2006-07-17 Complexes carbene-metal n-heterocycliques immobilisables comportant des groupes alcoxysilyle Ceased WO2007017047A1 (fr)

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DE102005037500A DE102005037500A1 (de) 2005-08-09 2005-08-09 Immobilisierbare N-heterozyklische Carben-Metall-Komplexe mit Alkoxysilylgruppen
DE102005037500.6 2005-08-09

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CN102741262A (zh) * 2009-10-28 2012-10-17 香港大学 用于治疗癌症的含有环金属n-杂环卡宾络合物的药物组合物
CN102741262B (zh) * 2009-10-28 2014-08-27 香港大学 用于治疗癌症的含有环金属n-杂环卡宾络合物的药物组合物
WO2011050574A1 (fr) * 2009-10-28 2011-05-05 The University Of Hong Kong Composition pharmaceutique contenant des complexes cyclométallés de carbènes n-hétérocycliques pour le traitement du cancer
US9427731B2 (en) 2009-12-03 2016-08-30 Materia, Inc. Supported olefin metathesis catalysts
US9249466B2 (en) 2010-01-08 2016-02-02 Agency For Science, Technology And Research Methods and compositions for treating cancer
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JP7048945B2 (ja) 2016-12-07 2022-04-06 国立研究開発法人産業技術総合研究所 有機金属錯体触媒
CN110049815B (zh) * 2016-12-07 2022-04-12 国立研究开发法人产业技术综合研究所 有机金属络合物催化剂
JP7231170B2 (ja) 2016-12-07 2023-03-01 国立研究開発法人産業技術総合研究所 有機金属錯体触媒
JPWO2018105672A1 (ja) * 2016-12-07 2019-10-24 国立研究開発法人産業技術総合研究所 有機金属錯体触媒
CN110062655A (zh) * 2016-12-07 2019-07-26 国立研究开发法人产业技术综合研究所 有机金属络合物催化剂
CN110049815A (zh) * 2016-12-07 2019-07-23 国立研究开发法人产业技术综合研究所 有机金属络合物催化剂
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CN110062655B (zh) * 2016-12-07 2022-08-16 国立研究开发法人产业技术综合研究所 有机金属络合物催化剂
JP2022078118A (ja) * 2016-12-07 2022-05-24 国立研究開発法人産業技術総合研究所 有機金属錯体触媒
WO2018105671A1 (fr) * 2016-12-07 2018-06-14 国立研究開発法人産業技術総合研究所 Catalyseur complexe organométallique
JPWO2018105671A1 (ja) * 2016-12-07 2019-10-24 国立研究開発法人産業技術総合研究所 有機金属錯体触媒
JP7066125B2 (ja) 2016-12-07 2022-05-13 国立研究開発法人産業技術総合研究所 有機金属錯体触媒
JP7032769B2 (ja) 2018-08-31 2022-03-09 エヌ・イーケムキャット株式会社 クロスカップリング反応用触媒
JPWO2020045476A1 (ja) * 2018-08-31 2021-09-02 エヌ・イーケムキャット株式会社 クロスカップリング反応用触媒
WO2020045476A1 (fr) * 2018-08-31 2020-03-05 エヌ・イー ケムキャット株式会社 Catalyseur de réaction de couplage croisé
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