WO2013046108A1 - Ruthenium or osmium complex, method for its preparation and use thereof - Google Patents

Ruthenium or osmium complex, method for its preparation and use thereof Download PDF

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WO2013046108A1
WO2013046108A1 PCT/IB2012/055058 IB2012055058W WO2013046108A1 WO 2013046108 A1 WO2013046108 A1 WO 2013046108A1 IB 2012055058 W IB2012055058 W IB 2012055058W WO 2013046108 A1 WO2013046108 A1 WO 2013046108A1
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aryl
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Tomasz WDOWIK
Cezary SAMOJŁOWICZ
Magdalena JAWICZUK
Karol Grela
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Instytut Chemii Organicznej Polskiej Akademii Nauk
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Instytut Chemii Organicznej Polskiej Akademii Nauk
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Priority to CN201280046966.8A priority Critical patent/CN104185506A/en
Priority to JP2014531366A priority patent/JP5908093B2/en
Priority to US14/346,865 priority patent/US20150298111A1/en
Priority to EP12781456.4A priority patent/EP2760581B1/en
Priority to SG11201400937SA priority patent/SG11201400937SA/en
Publication of WO2013046108A1 publication Critical patent/WO2013046108A1/en
Priority to IL231682A priority patent/IL231682A0/en
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
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    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
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    • C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
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    • C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
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    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/28—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • the present invention relates to novel complexes of metals that act as pre(catalysts), a method of manufacturing them as well as their use in the metathesis, isomerisation and cycloisomerisation of oleofins, a method of manufacturing them as well as their use in olefin metathesis, isomerisation and cycloisomerisation reactions, as well as in olefin as well as in reakcji hydrogen transfer.
  • the present invention is useful in broadly understood organic synthesis.
  • Complexes defined by Formula 1, according to the present invention are useful in a broad range of reactions.
  • a good result may be obtained by conducting both numerous metathesis ring closure reactions, as well as homometatheses, cross metatheses as well as well as metatheses of the "alkene-alkyne" (ene-yne), ring-opening polymerisation reactions (ROMP), olefin isomerisation reactions, olefin cycloisomerisation reactions as well as hydrogen transfer reactions.
  • the high polarity of the compounds being the subject of the present invention also makes it easier to remove ruthenium compounds from the reaction products, which is very significant in the synthesis of compounds for the pharmaceutical industry.
  • the subject of the present invention are novel metal complexes, containing a nitroanion group defined by Formula 1:
  • M denotes ruthenium or osmium
  • L 1 and L 2 denote neutral ligands
  • X denotes an anionic ligand
  • Z denotes a nitrogen atom
  • Y denotes an oxygen atom
  • R l , R 2 denote, independently of one another, a hydrogen atom, a fluoride atom, Ci-C 2 5 alkyl, C t - C25 perfiuoroalkyl, C 2 -C 25 alkene, C3-C7 cycloalkyl, C 2 -C 25 alkenyl, C 3 -C 2 5 cycloalkenyl, C 2 -C 2 5 alkynyl, C 3 -C 2 5 cycloalkynyl, C[-C 2 5 alkoxyl , C 5 -C 2 4 aryl, C 5 -C o heteroaryl, or a 3-12 membered heterocycle wherein the alkyl groups may be joined together in a ring, preferentially a hydrogen, a nitro (-N0 2 ), cyanide (-CN), carboxyl (-COOH), carboxyl (-COOR'), amido (-CONR ' 2 ), sulphonyl (-
  • R of Formula 1 denotes a hydrogen atom or methyl group; R denotes a hydrogen atom and the
  • each R 5 denotes, independently of one another, C1-C12 alkyl, C 3 -C i 2 cycloalkyl, C 5 -C 2 o aryl, 5- 12 membered heteroaryl;
  • each R , R , R , R and R denotes, independently of one another, a hydrogen atom, C [-Ci 2 alkyl, C 3 -C i 2 cycloalkyl, C 2 -Ci 2 alkenyl or C5-Q0 aryl which may be substituted with at least one C i-Ci 2 alkyl, C i-C i 2 perhaloalkyl, Ci-C t2 alkoxyl or fluoride atom, and groups R 6 , R 7 , R 8 , R 9 and R 10 may possibly be interconnected.
  • Carbene ligands may be classically coordinated, as in structures 2a-2h, or in a non-classic fashion (abnormal carbenes", see: Chem. Rev. 2009, 109, 3445) as in structures 2i-2p.
  • the anionic ligand X of Formula 1 denotes a chlorine atom
  • neutral ligand L 1 denotes -P(R 5 ) 3 in which substituent R 5 has a meaning as set out above; and neutral ligand L denotes ligands defined by Formula 2a or 2b:
  • the subject of the present invention is also a method of producing complexes of metals defined by Formula 1, which encompasses the reaction of compounds defined by Formula 3
  • R 1 , R2 , Z, Y have meanings as defined above
  • R 3 , R 13 , R 14 denote, independently of one another, a hydrogen atom, a fluoride atom, Ci-C 2 5 alkyl, Ci-C 25 perfluoroalkyl, C 2 -C 2 5 alkene, C 3 -C 7 cycloalkyl, C 2 -C 25 alkenyl, C 3 -C 25 cycloalkenyl, C 2 -C 2 5 alkynyl, C -C 2 5 cycloalkynyl, Ci-C 2 5 alkoxyl, C5-Q4 aryl, heteroaryl C5-C 2 o, or a 3-12 membered heterocycle wherein the alkyl groups may be joined together in a ring, preferentially a hydrogen, a nitro group (-N0 2 ), a cyanide group (-CN), carboxyl (-COOH), carboxyl (-COOR'
  • R 1 denotes hydrogen, a fluoride atom, C 1-C 12 alkyl, C3-C 12 cycloalkyl, C 2 -Ci 2 alkenyl, C3-C 12 cycloalkenyl, C2-C 12 alkynyl, C 3 -Ci 2 cycloalkynyl, C1-C 12 alkoxyl, C5-C20 aryl, C5-C 2 o heteroaryl, or a 3-12 membered heterocycle;
  • M denotes ruthenium or osmium
  • L 1 , L 2 and L 3 independently of one another, denote neutral ligands
  • X 1 and X 2 independently of one another, denote an anionic ligand
  • R 1 1 has the same meaning as R 1 of Formula 1;
  • R 12 denotes a hydrogen atom, C 5 -C 2 o aryl, C5-C20 heteroaryl, vinyl or allenyl.
  • the reaction is carried out over a period from 1 min. do 250 h, at a temperature in the range from 0 to 150°C.
  • the reaction is carried out in a chlorineinated solvent or in aromatic hydrocarbons, or in protic or aprotic solvents, such as alcohols or ketones or in mixtures thereof.
  • the reaction is carried out in a solvent selected from among methylene chloride and/or toluene.
  • the present invention also relates to the use of complexes of ruthenium defined by Formula 1 as (pre)catalysts in metathesis reactions.
  • ruthenium complexes defined by Formula 1 are used as (pre)catalysts in metathesis ring closing reactions, homometatheses, cross-metatheses, "alkene-alkyne” metathesis (ene-yne) ROMP polymerisations as well as olefin cyclomerisation reactions.
  • a fluoride atom denotes an element selected from among F, CI, Br, or I.
  • the term “carbene” denotes a molecule containing a neutral carbon atom with a valence number of two and two unpaired valence electrons.
  • the term “carbene” also encompasses carbene analogues in which the carbon atom is substituted by another chemical elements such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulphur, selenium and tellurium.
  • alky refers to a saturated, linear, or branched hydrocarbon substituent with the indicated number of carbon atoms.
  • alkyl substituent are -methyl, -ethyl, -n- propyl, -rc-butyl, -M-pentyl, -n-hexyl, -M-heptyl, - «-octyl, - «-nonyl, and - «-decyl.
  • Representative branched -(Ci-Cio)alkyls encompass -isopropyl, -sec-butyl, -isobutyl, -teri-butyl, -isopentyl, - neopentyl, -1-methylbutyl, -2-methylbutyl, -3-methylbutyl, -1 ,1 -dimethylpropyl, -1,2- dimethylpropyl, -1-methylpentyl, -2-methylpentyl, -3-methylpentyl, -4-methylpentyl, -1- ethylbutyl, -2-ethylbutyl, -3-ethylbutyl, -1 , 1 -dimethylbutyl, -1 ,2-dimethylbutyl, -1 ,3- dimethylbutyl, -2,2-dimethylbutyl, -2,3-dimethylbutyl, -3,3-
  • peril uoroalkyl denotes an alkyl group as defined above in which all hydrogen atoms have been replaced by identical or different atomy fluoride atoms.
  • cycloalkyl refers to a saturated mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms. Examples of cycloalkyl substituents are -cyclopropyl, - cyclobutyl, -cyclopentyl, -cyclohexyl, -cycloheptyl, -cyclooctyl, -cyclononyl, -cyclodecyl, and the like.
  • alkenyl refers to an unsaturated, linear, or branched acyclic hydrocarbon substituent with the indicated number of carbon atoms and containing at least one double carbon- carbon bond.
  • alkenyl substituents are: -vinyl, -allyl, -1-butenyl, -2-butenyl, - isobutylenyl, -1 -pentenyl, -2-pentenyl, -3 -methyl- 1-butenyl, -2-methyl-2-butenyl, -2,3 -dimethyl - 2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1-he tenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, - 2-octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3-nonenyl, -1-decenyl, -2-decenyl, -3-decenyl and the like.
  • cycloalkenyl refers to an unsaturated mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms and containing at least one double carbon- carbon bond.
  • Examples of cycloalkenyl substituents are -cyclopentenyl, -cyclopentadienyl, - cyclohexenyl, -cyclohexadienyl, -cycloheptenyl, -cycloheptadienyl, -cycloheptatrienyl, -cyclooctenyl, -cyclooctadienyl, -cyclooctatrienyl, -cyclooctatetraenyl, -cyclononenyl, - cyclononadienyl, -cyclodecenyl, -cyclodekadienyl and the like.
  • alkynyl refers to an unsaturated, linear, or branched acyclic hydrocarbon substituent with the indicated number of carbon atoms and containing at least one triple carbon- carbon bond.
  • alkynyl substituents are -acethylenyl, -propynyl, -1-butynyl, -2- butynyl, -1-pentynyl, -2-pentynyl, -3-methyl- 1-butynyl, -4-pentynyl, -1-hexynyl, -2-hexynyl, -5- hexynyl and the like.
  • cycloalkynyl refers to saturated mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms and containing at least one triple carbon-carbon bond.
  • Examples of cycloalkynyl substituents are -cyclohexynyl, -cycloheptynyl, -cyclooctynyl, and the like.
  • aryl refers to an aromatic mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms.
  • aryl substituents are -phenyl, -tolyl, -xylyl, - naphthyl and the like.
  • heteroaryl refers to an aromatic mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms in which at least one the carbon atom has been replaced by a heteroatom selected from among O, N and S.
  • heteroaryl substituents are -furyl, - thienyl,- imidazolyl, -oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, -oxadiazolyl, -thiadiazolyl, - tetrazolyl, -pirydyl, -pirymidyl, -triazynyl, -indolyl, -benzo[b]furyl, -benzo[b]thienyl, -indazolyl, -benzoimidazolyl, -azaindolyl, -quinolyl, -isoquinolyl, -carbazolyl and the like.
  • heterocycle refers to saturated or partially unsaturated mono- or polycyclic hydrocarbon substituents, with the indicated number of carbon atoms in which at least one the carbon atom has been replaced by heteroatom selected from among O, N and S.
  • heterocyclic substituents are -furyl, -thiophenyl, -pyrolyl, -oxazolyl, -imidazolyl, -thiazolyl, - isoxazolyl, -pirazolyl, -isothiazolyl, -triazynyl, -pyrolidynonyl, -pyrolidynyl, -hydantoinyl, - oxiranyl, -oxethanyl, -tetrahydrofuranyl, -tetrahydrothiophenyl, -quinolinyl, -isoquinolinyl, - chromonyl, -cumarynyl,
  • neutral ligands refers to uncharged substituents, capable of coordinating with a metallic centre (ruthenium atom).
  • ligands may be: amines, phosphines and their oxides, alkyl and alkane phosphorines and phosphoranes, arsines and their oxides, ethers, alkyl and aryl sulphides, coordinated hydrocarbons, alkyl and aryl halides.
  • indenyl refers to an unsaturated hydrocarbon substituent with an inden skeleton (benzocyclopentadiene).
  • heteroindenyl refers to an indenyl substituent, defined above in which at least one carbon atom is replaced with a heteroatom from a group encompassing: nitrogen, oxygen and sulphur.
  • an anionic ligand refers to a substituent capable of coordinating with a metallic centre (ruthenium atom) possessing a charge capable of the partial or full compensation of the metallic centre charge.
  • ligands may be: fluoride, chloride, bromide, iodide, cianide, cyanin and thiocyanin anions, carboxylic acid anions, alcohol anions, anions of phenols, thiols and thiophenols, anions of hydrocarbons with a displaced charge (i.e. cyclopentadiene), anions of (organo)sulphuric and (organo)phosphoric acids as well as their esters (such as i.e.
  • alkylsulphonic and arylsulphonic acids anions of alkylsulphonic and arylsulphonic acids, anions of alkylphosphoric and arylphosphoric acids, anions of alkyl and aryl esters of sulphuric acid, anions of alkyl and aryl estersof phosphoric acids, anions of alkyl and aryl esters of alkylphosphoric and arylphosphoric acids).
  • an anionic ligand may possess linked L , L , L groups such as a katechol anion, an acetylacetone anion, a salicylic aldehyde anion.
  • Anionic ligands (X 1 , X 2 ) as well as neutral ligands (L 1 , L 2 , L 3 ) may be linked forming polydentate ligands, for example: bidentate ligands (X 1 , X 2 ), tridentate ligands (X 1 , X 2 , L 1 ), tetradentate ligands (X 1 , X 2 , L 1 , L 2 ), bidentate ligands (X 1 , L 1 ), tridentate ligands (X 1 , L l , L 2 ), tetradentate ligands (X 1 , L 1 , L 2 , L 3 ), bidentate ligands (L 1 , L 2 ), tri
  • the resulting solution were mixed at room temperature for 20 hours. From this time, all subsequent operations were performed in the open air, without the need for a protective argon atmosphere.
  • the reaction mixture was concentrated in an evaporator and loaded onto a chromatography column packed with a silica gel. The column was developed with an ethyl acetate-cyclohexane solution (10% v/v), collecting the green fraction. After evaporating off the solvent, we obtained complex la as an olive, microcrystalline solid (52.6 mg, 55% efficiency).
  • the resulting solution were mixed at room temperature for about 15 min. From this time, all subsequent operations were performed in the open air, without the need for a protective argon atmosphere.
  • the reaction mixture was concentrated in an evaporator and loaded onto a chromatography column packed with a silica gel. The column was developed with an ethyl acetate-cyclohexane solution (10% v/v), collecting the green fraction. After evaporating off the solvent, we obtained complex lb as an olive, microcrystalline solid (93.3 mg, 66% efficiency).
  • reaction mixture was concentrated in an evaporator and loaded onto a chromatography column packed with a silica gel. The column was developed with an ethyl acetate-cyclohexane solution (10% v/v), collecting the green fraction. After evaporating off the solvent, we obtained complex lc as an olive, microcrystalline solid (9.5 mg, 50% efficiency).
  • reaction mixture was concentrated in an evaporator and loaded onto a chromatography column packed with a silica gel.
  • the column was developed with an ethyl acetate-cyclohexane solution (10% v/v), collecting the green fraction. After evaporating off the solvent, we obtained complex Id as an olive, microcrystalline solid (83.1 mg, 52% efficiency).
  • Procedure A in a Schlenk vessel, we placed a diene solution (48.4 mg, 0.20 mmol) in toluene (2 ml), we added hexachloroethane (1.9 mg, 4% mo i), and next, the catalyst la (1.6 mg, l% mo i). The vessel contents were mixed at a temperature of 80°C for 2 h. The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product metathesis was 100%.
  • Procedure B in a Schlenk vessel, we placed a diene solution (48.0 mg, 0.20 mmol) in toluene (2 ml), we added chlorotrimethylsilane (0.9 mg, 4% mo i), and next, the catalyst la (1.6 mg, l% mo i).
  • the vessel contents were mixed at a temperature of 80°C for 2 h.
  • the raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product metathesis was 85%.
  • Procedure C in a Schlenk vessel, we placed a diene solution (31.2 mg, 0.13 mmol) in carbon tetrachloride (0.6 ml), and next we added catalyst lb (5.1 mg, 5% mo i). The vessel contents were mixed at a temperature of 60°C for 4 h The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product metathesis was 98%.
  • Procedure D in a Schlenk vessel, we placed a diene solution (30.7 mg, 0.13 mmol) in carbon tetrachloride (0.6 ml), and next we added catalyst la (5.0 mg, 5% mo i). The vessel contents were mixed at a temperature of 60°C for 2 h. The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product metathesis was 100%.
  • Example XVIII Production of polidicyclopentadiene: a flask was loaded with dicyclopentadiene (132 mg, 1.0 mmol) in toluene (5 mL) and mixed at room temperature. Next, we added a chlorotrimethylsilane solution (1.1 mg, l% mo i) and catalyst la (0.2 mg, 0.025% mo i in toluene and the flask contents were mixed at the same temperature for 10 min. Next, we supplemented the flask with toluene and brought it to boiling temp, in order to wash off the unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure at a temperature of 100 °C for 12 h The conversion of dicyclopentadiene was 99%.
  • Example XIX In a Schlenk vessel, we placed a solution of catalyst la (15.7 mg, 2% mo i) in tetrahydrofuran (2.5 ml) and we added sodium hydride (2.8 mg, 7% mo i). To this mixture we then added acetophenone (120.3 mg, 1.0 mmol) and isopropyl alcohol (2.5 ml). The vessel contents were mixed at a temperature of 70 °C for 5 h. The raw mixture was purified using column chromatography on a silica gel (elution with cyclohexane: ethyl acetate 20:1). We obtained 95 mg of a liquid product (efficiency 78%).

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Abstract

The subject of the present invention are novel metal complexes defined by Formula (1): The present invention also relates to methods of producing said novel metal complexes defined by Formula (1) as well as their uses.

Description

A complex of ruthenium or osmium, a method of producing it and its use
The present invention relates to novel complexes of metals that act as pre(catalysts), a method of manufacturing them as well as their use in the metathesis, isomerisation and cycloisomerisation of oleofins, a method of manufacturing them as well as their use in olefin metathesis, isomerisation and cycloisomerisation reactions, as well as in olefin as well as in reakcji hydrogen transfer. The present invention is useful in broadly understood organic synthesis.
The use of olefin metathesis in organic synthesis has recently seen much progress. The state of the art reveals several carbene complexes of mthenium acting as (pre)catalysts which possess both high activity in metathesis reactions of various kinds, as well as a broad tolerance of functional groups. The above combination of properties warrants the utility of these types of (pre)catalysts in organic synthesis.
From the point of view of practical use, particularly on an industrial scale, it is very desirable that such mthenium complexes are stable, for extended periods at elevated temperatures, and may be stored and/or purified and/or used without a protective gas atmosphere. It is also important that these catalysts exhibit variable reactivity, depending on the reaction conditions, and that they are easy to remove after the reaction.
Many complexes of mthenium active in olefin metathesis have been disclosed (see: Org. Lett.
1999, /, 953-956; J. Chem. Soc. Chem. Commitn. 1999, 601 -602). It is also known that increased stability is connected with decreased catalytic activity (for comparison: J. Amer. Chem. Soc.
2000, 122, 8168-8179; Tetrahedron Lett. 2000, 41, 9973-9976). These types of advantages and limitathions have also been noted i the case of (pre)catalysts activated by steric or electron factors of the benzylidene ligands (for a comparison of catalytic activity see: Angew. Chem. Int. Ed. 2002, 114, 4210-4212; Angew. Chem. Int. Ed. 2002, 114, 2403-2405).
The effect of anionic ligands has also been demonstrated (see: Angew. Chem. Int. Ed. 2007, 46, 7206-7209; Organometallics, 2010, 29, 6045-6050; OrganometaUics, 2011, 30, 3971-3980) as well as of NHC ligands (see: Chem. Rev. 2010, 110, 1746-1787; Chem. Rev. 2009, 109, 3708- 3742) on the activity and selectivity of (pre)catalysts. From these reports, it stems that the exchange of a chloride ligand for an oxyacid residue increases the stability of the (pre)catalyst.
Unexpectedly it was shown that the novel ruthenium complexes according to the present invention defined by Formula 1 :
Figure imgf000003_0001
Formula 1
which contains a chelate ring formed by an oxygen atom are thermally stable and exhibit good catalytic activity. Additionally, these compounds significantly alter the selectivity of the reaction depending on the use of: a solvent and/or the Addition of an acid or halide derivatives of alkanes or halide derivatives of silanes or N-haloimides or N-haloamides; which enables the control over the catalytic processes through the exchange of these factors.
Complexes defined by Formula 1, according to the present invention are useful in a broad range of reactions. A good result may be obtained by conducting both numerous metathesis ring closure reactions, as well as homometatheses, cross metatheses as well as well as metatheses of the "alkene-alkyne" (ene-yne), ring-opening polymerisation reactions (ROMP), olefin isomerisation reactions, olefin cycloisomerisation reactions as well as hydrogen transfer reactions.
The high polarity of the compounds being the subject of the present invention also makes it easier to remove ruthenium compounds from the reaction products, which is very significant in the synthesis of compounds for the pharmaceutical industry.
The subject of the present invention are novel metal complexes, containing a nitroanion group defined by Formula 1:
Figure imgf000004_0001
Formula 1
in which:
M denotes ruthenium or osmium;
L1 and L2 denote neutral ligands;
X denotes an anionic ligand;
Z denotes a nitrogen atom;
Y denotes an oxygen atom;
Rl, R2 denote, independently of one another, a hydrogen atom, a fluoride atom, Ci-C25 alkyl, Ct- C25 perfiuoroalkyl, C2-C25 alkene, C3-C7 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C[-C25 alkoxyl, C5-C24 aryl, C5-C o heteroaryl, or a 3-12 membered heterocycle wherein the alkyl groups may be joined together in a ring, preferentially a hydrogen, a nitro (-N02), cyanide (-CN), carboxyl (-COOH), carboxyl (-COOR'), amido (-CONR' 2), sulphonyl (-S02R ), formyl (-CHO), sulphonoamido (-S02NR'2), or ketone (-COR') group, in which R has the following meaning: C1-C5 alkyl, C 1-C5 perfiuoroalkyl, C5-C24 aryl.
1 2 In a preferable embodiment R of Formula 1 denotes a hydrogen atom or methyl group; R denotes a hydrogen atom and the
anionic ligand X denotes a fluoride atom, a -CN, -SCN, -OR4, -SR4, -0(C=0)R4, -0(S02)R4, or - OSiR3 4 group, where R4 denotes an Ci-Ci2 alkyl, C3-Ci2 cycloalkyl, C2-Ci2 alkenyl, or Cs-C2o aryl, which may be substituted with at least one Ci-Ci2 alkyl, Ci-C[ perhaloalkyl, Ci-Ci2 alkoxyl or fluoride atom; and the neutral ligands Ll and L2 are selected, independently of one another, from a group encompassing -P(R5)3, -P(OR5)3 or N-heterocyclic carbene ligands denoted by Formulae 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, 2j, 2k, 21, 2m, 2n, 2o or 2p: R7 R6. N N- R8
Figure imgf000005_0001
Formula 2 c
Formula 2b Formula 2d
Figure imgf000005_0002
Formula 2e Formula 2f Formula 2g Formula 2h
Formula 2i
Formu
Figure imgf000005_0003
Formula 2m Formula 2p
Formula 2n Formula 2o
where: each R5 denotes, independently of one another, C1-C12 alkyl, C3-C i2 cycloalkyl, C5-C2o aryl, 5- 12 membered heteroaryl;
6 7 8 9 10
each R , R , R , R and R denotes, independently of one another, a hydrogen atom, C [-Ci2 alkyl, C3-C i2 cycloalkyl, C2-Ci2 alkenyl or C5-Q0 aryl which may be substituted with at least one C i-Ci2 alkyl, C i-C i2 perhaloalkyl, Ci-C t2 alkoxyl or fluoride atom, and groups R6, R7, R8, R9 and R10 may possibly be interconnected. Carbene ligands may be classically coordinated, as in structures 2a-2h, or in a non-classic fashion (abnormal carbenes", see: Chem. Rev. 2009, 109, 3445) as in structures 2i-2p.
In another preferable embodiment, the anionic ligand X of Formula 1 denotes a chlorine atom; and
neutral ligand L1 denotes -P(R5)3 in which substituent R5 has a meaning as set out above; and neutral ligand L denotes ligands defined by Formula 2a or 2b:
Figure imgf000006_0001
Formula 2a Formula 2b
in which substituents R6, R7, R8 and R9 mean as defined above.
The subject of the present invention is also a method of producing complexes of metals defined by Formula 1, which encompasses the reaction of compounds defined by Formula 3
Figure imgf000006_0002
Formula 3
in which R 1 , R2 , Z, Y have meanings as defined above, whereas R 3 , R 13 , R 14 denote, independently of one another, a hydrogen atom, a fluoride atom, Ci-C25 alkyl, Ci-C25 perfluoroalkyl, C2-C25 alkene, C3-C7 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C -C25 cycloalkynyl, Ci-C25 alkoxyl, C5-Q4 aryl, heteroaryl C5-C2o, or a 3-12 membered heterocycle wherein the alkyl groups may be joined together in a ring, preferentially a hydrogen, a nitro group (-N02), a cyanide group (-CN), carboxyl (-COOH), carboxyl (-COOR'), amido (- CONR'2), sulphonyl (-S02R ), formyl (-CHO), sulphonoamido (-S02NR'2), ketone (-COR'), in which R has the following meaning: C 1-C5 alkyl, C 1-C5 perfluoroalkyl, C5-C24 aryl;
R1 denotes hydrogen, a fluoride atom, C 1-C 12 alkyl, C3-C 12 cycloalkyl, C2-Ci2 alkenyl, C3-C 12 cycloalkenyl, C2-C 12 alkynyl, C3-Ci2 cycloalkynyl, C1-C 12 alkoxyl, C5-C20 aryl, C5-C2o heteroaryl, or a 3-12 membered heterocycle;
with carbene complexes of ruthenium defined by Formulae 4a, 4b, 4c or 4d:
Figure imgf000007_0001
Formula 4 Formula 4b Formula 4c Formula 4d
in which
M denotes ruthenium or osmium;
L1, L2 and L3, independently of one another, denote neutral ligands;
X1 and X2, independently of one another, denote an anionic ligand;
R1 1 has the same meaning as R1 of Formula 1;
R12 denotes a hydrogen atom, C5-C2o aryl, C5-C20 heteroaryl, vinyl or allenyl.
Preferentially, the reaction is carried out over a period from 1 min. do 250 h, at a temperature in the range from 0 to 150°C.
Preferentially, the reaction is carried out in a chlorineinated solvent or in aromatic hydrocarbons, or in protic or aprotic solvents, such as alcohols or ketones or in mixtures thereof.
Preferentially, the reaction is carried out in a solvent selected from among methylene chloride and/or toluene.
The present invention also relates to the use of complexes of ruthenium defined by Formula 1 as (pre)catalysts in metathesis reactions. Preferentially, ruthenium complexes defined by Formula 1 are used as (pre)catalysts in metathesis ring closing reactions, homometatheses, cross-metatheses, "alkene-alkyne" metathesis (ene-yne) ROMP polymerisations as well as olefin cyclomerisation reactions..
The term "a fluoride atom" denotes an element selected from among F, CI, Br, or I. The term "carbene" denotes a molecule containing a neutral carbon atom with a valence number of two and two unpaired valence electrons. The term "carbene" also encompasses carbene analogues in which the carbon atom is substituted by another chemical elements such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulphur, selenium and tellurium.
The term "alky!" refers to a saturated, linear, or branched hydrocarbon substituent with the indicated number of carbon atoms. Examples of an alkyl substituent are -methyl, -ethyl, -n- propyl, -rc-butyl, -M-pentyl, -n-hexyl, -M-heptyl, -«-octyl, -«-nonyl, and -«-decyl. Representative branched -(Ci-Cio)alkyls encompass -isopropyl, -sec-butyl, -isobutyl, -teri-butyl, -isopentyl, - neopentyl, -1-methylbutyl, -2-methylbutyl, -3-methylbutyl, -1 ,1 -dimethylpropyl, -1,2- dimethylpropyl, -1-methylpentyl, -2-methylpentyl, -3-methylpentyl, -4-methylpentyl, -1- ethylbutyl, -2-ethylbutyl, -3-ethylbutyl, -1 , 1 -dimethylbutyl, -1 ,2-dimethylbutyl, -1 ,3- dimethylbutyl, -2,2-dimethylbutyl, -2,3-dimethylbutyl, -3,3-dimethylbutyl, -1 -methylhexyl, -2- methylhexyl, -3-methylhexyl, -4-methylhexyl, -5-methylhexyl, -1 ,2-dimethylpentyl, -1 ,3- dimethylpentyl, -1 ,2-dimethylhexyl, - 1,3-dimethylhexyl, -3,3-dimethylhexyl, -1,2- dimethylheptyl, -1 ,3-dimethylheptyl, and -3,3-dimethylheptyl and the like. The term "alkoxyl" refers to an alkyl substituent as defined above attached via an oxygen atom.
The term "peril uoroalkyl" denotes an alkyl group as defined above in which all hydrogen atoms have been replaced by identical or different atomy fluoride atoms.
The term "cycloalkyl" refers to a saturated mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms. Examples of cycloalkyl substituents are -cyclopropyl, - cyclobutyl, -cyclopentyl, -cyclohexyl, -cycloheptyl, -cyclooctyl, -cyclononyl, -cyclodecyl, and the like. The term "alkenyl" refers to an unsaturated, linear, or branched acyclic hydrocarbon substituent with the indicated number of carbon atoms and containing at least one double carbon- carbon bond. Examples of alkenyl substituents are: -vinyl, -allyl, -1-butenyl, -2-butenyl, - isobutylenyl, -1 -pentenyl, -2-pentenyl, -3 -methyl- 1-butenyl, -2-methyl-2-butenyl, -2,3 -dimethyl - 2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1-he tenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, - 2-octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3-nonenyl, -1-decenyl, -2-decenyl, -3-decenyl and the like.
The term "cycloalkenyl" refers to an unsaturated mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms and containing at least one double carbon- carbon bond. Examples of cycloalkenyl substituents are -cyclopentenyl, -cyclopentadienyl, - cyclohexenyl, -cyclohexadienyl, -cycloheptenyl, -cycloheptadienyl, -cycloheptatrienyl, -cyclooctenyl, -cyclooctadienyl, -cyclooctatrienyl, -cyclooctatetraenyl, -cyclononenyl, - cyclononadienyl, -cyclodecenyl, -cyclodekadienyl and the like.
The term "alkynyl" refers to an unsaturated, linear, or branched acyclic hydrocarbon substituent with the indicated number of carbon atoms and containing at least one triple carbon- carbon bond. Examples of alkynyl substituents are -acethylenyl, -propynyl, -1-butynyl, -2- butynyl, -1-pentynyl, -2-pentynyl, -3-methyl- 1-butynyl, -4-pentynyl, -1-hexynyl, -2-hexynyl, -5- hexynyl and the like.
The term "cycloalkynyl" refers to saturated mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms and containing at least one triple carbon-carbon bond. Examples of cycloalkynyl substituents are -cyclohexynyl, -cycloheptynyl, -cyclooctynyl, and the like.
The term "aryl" refers to an aromatic mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms. Examples of aryl substituents are -phenyl, -tolyl, -xylyl, - naphthyl and the like.
The term "heteroaryl" refers to an aromatic mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms in which at least one the carbon atom has been replaced by a heteroatom selected from among O, N and S. Examples of heteroaryl substituents are -furyl, - thienyl,- imidazolyl, -oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, -oxadiazolyl, -thiadiazolyl, - tetrazolyl, -pirydyl, -pirymidyl, -triazynyl, -indolyl, -benzo[b]furyl, -benzo[b]thienyl, -indazolyl, -benzoimidazolyl, -azaindolyl, -quinolyl, -isoquinolyl, -carbazolyl and the like.
The term "heterocycle" refers to saturated or partially unsaturated mono- or polycyclic hydrocarbon substituents, with the indicated number of carbon atoms in which at least one the carbon atom has been replaced by heteroatom selected from among O, N and S. Examples of heterocyclic substituents are -furyl, -thiophenyl, -pyrolyl, -oxazolyl, -imidazolyl, -thiazolyl, - isoxazolyl, -pirazolyl, -isothiazolyl, -triazynyl, -pyrolidynonyl, -pyrolidynyl, -hydantoinyl, - oxiranyl, -oxethanyl, -tetrahydrofuranyl, -tetrahydrothiophenyl, -quinolinyl, -isoquinolinyl, - chromonyl, -cumarynyl, -indolyl, -indolizynyl, -benzo[b]furanyl, -benzo[b]thiophenyl, - indazolyl, -purynyl, -4H-quinolizynyl, -isoquinolyl, -quinolyl, -phthalazynyl, -naphthyrydynyl, - carbazolyl, -β-carbolinyl and the like.
The term "neutral ligands" refers to uncharged substituents, capable of coordinating with a metallic centre (ruthenium atom). Examples of such ligands may be: amines, phosphines and their oxides, alkyl and alkane phosphorines and phosphoranes, arsines and their oxides, ethers, alkyl and aryl sulphides, coordinated hydrocarbons, alkyl and aryl halides.
The term "indenyl" refers to an unsaturated hydrocarbon substituent with an inden skeleton (benzocyclopentadiene).
The term "heteroindenyl" refers to an indenyl substituent, defined above in which at least one carbon atom is replaced with a heteroatom from a group encompassing: nitrogen, oxygen and sulphur.
The term "an anionic ligand" refers to a substituent capable of coordinating with a metallic centre (ruthenium atom) possessing a charge capable of the partial or full compensation of the metallic centre charge. Examples of such ligands may be: fluoride, chloride, bromide, iodide, cianide, cyanin and thiocyanin anions, carboxylic acid anions, alcohol anions, anions of phenols, thiols and thiophenols, anions of hydrocarbons with a displaced charge (i.e. cyclopentadiene), anions of (organo)sulphuric and (organo)phosphoric acids as well as their esters (such as i.e. anions of alkylsulphonic and arylsulphonic acids, anions of alkylphosphoric and arylphosphoric acids, anions of alkyl and aryl esters of sulphuric acid, anions of alkyl and aryl estersof phosphoric acids, anions of alkyl and aryl esters of alkylphosphoric and arylphosphoric acids).
* . . . - 1 2 3
Possibly, an anionic ligand may possess linked L , L , L groups such as a katechol anion, an acetylacetone anion, a salicylic aldehyde anion. Anionic ligands (X1, X2) as well as neutral ligands (L1, L2, L3) may be linked forming polydentate ligands, for example: bidentate ligands (X1, X2), tridentate ligands (X1, X2, L1), tetradentate ligands (X1, X2, L1, L2), bidentate ligands (X1, L1), tridentate ligands (X1, Ll, L2), tetradentate ligands (X1, L1, L2, L3), bidentate ligands (L1, L2), tridentate ligands (L1, L2, L3). Examples of such ligands are: a katechol anion, an aceylacetone anion as well as a salic lic aldehyde anion.
Figure imgf000011_0001
Formula 4a Formula 4b
Figure imgf000011_0002
Scheme 1
Formula 1
The examples below explain the production and use of the novel complexes.
Example I:
Synthesis of a catalyst defined by Formula la (according to Scheme I)
Figure imgf000012_0001
Formula la
Using a protective argon atmosphere in a Schlenk vessel, we placed a solid carbene metal complex defined by Formula 4a, in which M denotes ruthenium, X1 and X2 denote chlorine, L1 denotes tricyclohexylphosphine (PCy3), L2 denotes the NHC ligands defined by Formula 2a, in which R6 and R9 denote 2,4,6-trimethylphenyl, R7, R8 as well as R1 1 are hydrogen and R12 is phenyl (so-called Grubbs II-generation catalyst, 102 mg, 0.12 mmol), we added dry deoxygenated dichloromethane (2 ml). Next, we added the compound defined by Formula 3a:
Figure imgf000012_0002
Formula 3a
(13.1 mg, 0.15 mmol). The resulting solution were mixed at room temperature for 20 hours. From this time, all subsequent operations were performed in the open air, without the need for a protective argon atmosphere. The reaction mixture was concentrated in an evaporator and loaded onto a chromatography column packed with a silica gel. The column was developed with an ethyl acetate-cyclohexane solution (10% v/v), collecting the green fraction. After evaporating off the solvent, we obtained complex la as an olive, microcrystalline solid (52.6 mg, 55% efficiency). lH NMR (500 MHz, CDC13): d = 14.27 (d, J = 3 Hz, 1H), 7.02-6.90 (m, 4H), 6.42 (d, J = 3 Hz, 1H), 3.88-3.86 (m, 2H), 3.82-3.79 (m, 2H), 2.59 (s, 3H), 2.52 (s, 3H), 2.46 (s, 3H), 2.33 (s, 3H), 2.31 (s, 3H) 1.98 (s, 3H), 1.75-1.56 (m, 21 H), 1.1 1-1.00 (m, 9H), 0.92-0.85 (m, 3H);
l3C NMR (125 MHz, CDC13): d = 249.2, 219.3, 218.7, 138.8, 138.6, 138.4, 138.0, 137.6, 137.5, 136.3, 133.8, 130.4, 130.0, 129.9, 129.1 , 128.9, 51.6, 51.2, 35.6, 35.1, 33.1, 33.0, 29.3, 28.9, 27.8, 27.7, 27.6, 27.5, 27.0, 26.5, 26.3, 26.1, 21.2, 21.1, 19.3, 18.7, 18.6, 16.9; 1P NMR (202 MHz, CDC13): d = 34.2 (s, IP);
IR (KBr): 2925, 2850, 1813, 1512, 1483, 1430, 1379, 1266, 1169, 1041, 849, 743
MS (FD/FI): nVz found for the formula C4iH61 35ClN3O2P102Ru: 795.3 (M+).
Example II:
Synthesis of a catalyst defined by Formula lb (according to Scheme I)
Figure imgf000013_0001
Formula la
Using a protective argon atmosphere in a Schlenk vessel a solid carbene metal complex defined by Formula 4a, in which M denotes ruthenium, X1 and X2 denote chlorine, L1 denotes tricyclohexylphosphine (PCy3), L2 denotes the NHC ligands defined by Formula 2a, in which R6 and R9 denote 2,6-di(2-propyl)phenyl, R7, R8 as well as R1 ' are hydrogen and R12 phenyl (149 mg, 0.16 mmol), we added dry deoxygenated dichloromethane (2 ml). Next, we added the compound defined by Formula 3a (17.4 mg, 0.20 mmol). The resulting solution were mixed at room temperature for about 15 min. From this time, all subsequent operations were performed in the open air, without the need for a protective argon atmosphere. The reaction mixture was concentrated in an evaporator and loaded onto a chromatography column packed with a silica gel. The column was developed with an ethyl acetate-cyclohexane solution (10% v/v), collecting the green fraction. After evaporating off the solvent, we obtained complex lb as an olive, microcrystalline solid (93.3 mg, 66% efficiency).
Ή NMR (600 MHz, CDC13): d = 13.81 (d, J = 3 Hz, 1H), 7.36-7.10 (m, 6H), 6.29 (d, J = 3 Hz 1H), 4.20-4.10 (m, 1H), 4.10-4.00 (m, 1H), 4.00-3.80 (m, 3H), 3.75-3.65 (m, 1H), 3.65-3.55 (m 1H), 2.70-2.64 (m, 1H), 1.70-1.64 (m, 3H), 1.60-1.50 (m, 18H), 1.39-1.35 (m, 3H), 1.26-1.19 (m, 10H), 1.15-1.08 (m, 9H), 1,07-0.92 (m, 14H);
13C NMR (150 MHz, CDC13): d = 246.4, 222.2, 221.7, 148.64, 148.60, 148.5, 147.4, 137.5, 135.1, 130.0, 129.7, 129.0, 125.2, 124.2, 124.1, 123.9, 77.2, 77.0, 76.8, 54.0, 53.7, 33.2, 33.0, 29.6, 28.7, 28.5, 28.3, 27.9, 27.8, 27.2, 27.2, 26.9, 26.6, 26.3, 26.1, 23.4, 22.8, 22.0;
3lP NMR (202 MHz, CDC13): d = 35.3 (s, IP);
IR (KBr): 2962, 2927, 2851, 1431, 1414, 1383, 1326, 1269, 1238, 1 170, 1047, 803, 758, 734 cm '; MS (FD/FI): m/z found for the formula C47H73 35ClN3O2P102Ru: 879.3 (M+).
X-ray structural analysis for compound lb:
Figure imgf000014_0001
Example III:
Synthesis of a catalyst defined by Formula lc (according to Scheme I)
Figure imgf000015_0001
Formula lc
Using a protective argon atmosphere in a Schlenk vessel a solid carbene metal complex defined by Formula 4a, in which M denotes ruthenium, X1 and X2 denote chlorine, L1 denotes tricyclohexylphosphine (PCy3), L2 denotes the NHC ligands defined by Formula 2a, in which R6 and R9 denote 2,4,6-trimethylphenyl, R7, R8 as well as R1 1 are hydrogen and R12 is phenyl (so- called Grubbs II-generation catalyst, 20.7 mg, 0.024 mmol), we added dry deoxygenated dichloromethane (0.3 ml). Next, we added the compound defined by Formula 3b:
Figure imgf000015_0002
Formula 3b
(5 mg, 0.049 mmol). The resulting solution were mixed at room temperature for 20 hours. From this time, all subsequent operations were performed in the Open air, without the need for a protective argon atmosphere. The reaction mixture was concentrated in an evaporator and loaded onto a chromatography column packed with a silica gel. The column was developed with an ethyl acetate-cyclohexane solution (10% v/v), collecting the green fraction. After evaporating off the solvent, we obtained complex lc as an olive, microcrystalline solid (9.5 mg, 50% efficiency). 'H NMR (500 MHz, CDC13): 7.03 (s, 1H), 6.93 (s, 1H), 6.92 (s, 1H), 6.88 (s, 1H), 6.65 (s, 1H), 4.06-3.97 (m, 1H), 3.88-3.72 (m, 3H), 2.59 (s, 3H), 2.54 (s, 3H), 2.46 (s, 3H), 2.31 (s, 6H), 2.00 (s, 3H), 1.91 (s, 3H), 1.75-1.54 (m, 16H), 1.30-1.00 (m, 15H), 0.92-0.81 (m, 3H);
13C NMR (125 MHz, CDC13): d = 271.1, 271.0, 217.9, 217.2, 139.0, 138.7, 138.6, 138.3, 138.2, 138.0, 136.6, 133.6, 129.91, 129.85, 129.4, 128.6, 51.9, 51.5, 35.2, 33.6, 33.4, 28.9, 28.8, 27.9, 27.8, 27.6, 27.5, 26.9, 26.5, 21.1, 21.0, 19.2, 18.7, 18.5, 16.6; 3 lP NMR (202 MHz, CDC13): d = 27.0 (s, IP);
IR (film Z.CHC13): 2927, 2851, 1481, 1444, 1268, 1185, 850, 752, 624 cm"1;
MS (FD/FI): m/z found for the formula C42H6335ClN3O2Pl02Ru: 809.2 (M+).
Example IV:
Synthesis of a catalyst defined by Formula Id (according to Scheme I)
Figure imgf000016_0001
Formula 3d
Using a protective argon atmosphere in a Schlenk vessel a solid carbene metal complex defined by Formula 4a, in which M denotes ruthenium, X1 and X2 denote chlorine, Ll denotes tricyclohexylphosphine (PCy3), L2 denotes the NHC ligands defined by Formula 2a, in which R6 and R denote 2,6-di(2-propyl)phenyl, R , R as well as R are hydrogen and R phenyl (168 mg, 0.18 mmol), we added dry deoxygenated dichloromethane (2 ml). Next we added the compound defined by Formula 3b (22.7 mg, 0.23 mmol). The resulting solution were mixed at room temperature for about 15 min. From this time, all subsequent operations were performed in the open air, without the need for a protective argon atmosphere. The reaction mixture was concentrated in an evaporator and loaded onto a chromatography column packed with a silica gel. The column was developed with an ethyl acetate-cyclohexane solution (10% v/v), collecting the green fraction. After evaporating off the solvent, we obtained complex Id as an olive, microcrystalline solid (83.1 mg, 52% efficiency). lH NMR (600 MHz, CDC13): d = 7.40-7.10 (m, 6H), 6.67 (s, 1H), 4.10-4.00 (m, 1H), 3.98-3.87 (m, 2H), 3.68-3.54 (m, 3H), 3.75-3.65 (m, 1H), 3.65-3.55 (m, 1H), 2.41-2.32 (m, 1H), 2.16 (s, 3H), 1.77 (s, 3H), 1.69-1.59 (m), 1.57-1.48 (m), 1.39-1.29 (m), 1.25-1.20 (m), 1.20-1.12 (m), 1.11-1.02 (m), 1.01-0.91 (m).
13C NMR (150 MHz, CDC13): d = 268.3, 219.5, 219.0, 149.3, 148.8, 148.5, 147.3, 138.1, 130.4, 129.9, 128.9, 124.8, 124.2, 123.2, 77.2, 77.0, 76.8, 55.0, 53.9, 55.4, 35.3, 33.4, 30.9, 29.2, 28.8, 28.6, 28.2, 27.95, 27.88, 27.8, 27.1, 26.95, 26.87, 26.6, 26.4, 26.1, 25.9, 23.9, 23.2, 22.3, 21.7; 3 ,P NMR (202 MHz, CDC13): d = 26.4 (s, IP);
IR (film z CHC13): 2962, 2928, 2851, 1436, 1414, 1268, 1234, 1185, 803, 756, 616 cm"1
MS (FD/FI): m/z found for the formula C49H7535ClN3O2P102Ru: 893.4 (M+).
Examples of uses of compound 1 as catalyst in the metathesis reactions with ring closure, cross- metatheses, "alkene-alkyne" metatheses (ene-yne), as well as the olefin cycloisomerisation reaction.
Example V:
Figure imgf000017_0001
Scheme III
Procedure A: in a Schlenk vessel, we placed a diene solution (48.4 mg, 0.20 mmol) in toluene (2 ml), we added hexachloroethane (1.9 mg, 4%moi), and next, the catalyst la (1.6 mg, l%moi). The vessel contents were mixed at a temperature of 80°C for 2 h. The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product metathesis was 100%.
Procedure B: in a Schlenk vessel, we placed a diene solution (48.0 mg, 0.20 mmol) in toluene (2 ml), we added chlorotrimethylsilane (0.9 mg, 4%moi), and next, the catalyst la (1.6 mg, l%moi). The vessel contents were mixed at a temperature of 80°C for 2 h. The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product metathesis was 85%.
Procedure C: in a Schlenk vessel, we placed a diene solution (31.2 mg, 0.13 mmol) in carbon tetrachloride (0.6 ml), and next we added catalyst lb (5.1 mg, 5%moi). The vessel contents were mixed at a temperature of 60°C for 4 h The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product metathesis was 98%. Procedure D: in a Schlenk vessel, we placed a diene solution (30.7 mg, 0.13 mmol) in carbon tetrachloride (0.6 ml), and next we added catalyst la (5.0 mg, 5%moi). The vessel contents were mixed at a temperature of 60°C for 2 h. The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product metathesis was 100%.
Example VI:
Figure imgf000018_0001
In a Schlenk vessel, we placed a diene solution (74.1 mg, 0.29 mmol) in toluene (1.5 ml), we added camphorosulphonic acid (3.7 mg, 5%moi), and next, the catalyst la (12 mg, 5%moi). The vessel contents were mixed at a temperature of 80°C for 29 h The raw post-reaction mixture was analysed using gas chromatography. The conversion was 99%.
Example VII:
Figure imgf000018_0002
In a Schlenk vessel, we placed a diene solution (77.9 mg, 0.31 mmol) in toluene (1.5 ml), we added camphorosulphonic acid (5.1 mg, 7%moi), and next, the catalyst la (11.9 mg, 5%mol). The vessel contents were mixed at a temperature of 80°C for 14 h The raw post-reaction mixture was analysed using gas chromatography. The conversion was 100%.
Example VIII:
Figure imgf000018_0003
In a Schlenk vessel, we placed a diene solution (92.7 mg, 0.31 mmol) in toluene (1.5 ml), we added camphorosulphonic acid (4.4 mg, 6%raoi), and next, the catalyst la (12.0 mg, 5%moi). The vessel contents were mixed at a temperature of 80°C for 2 h. The raw post-reaction mixture was analysed using gas chromatography. The conversion was 100%.
Figure imgf000019_0001
In a Schlenk vessel, we placed a diene solution (76.0 mg, 0.31 mmol) in toluene (1.5 ml), we added camphorosulphonic acid (4.6 mg, 7%moi), and next, the catalyst la (11.9 mg, 5%moi). The vessel contents were mixed at a temperature of 80°C for 3 h The raw post-reaction mixture was analysed using gas chromatography. The conversion was 100%.
Example X:
Figure imgf000019_0002
In a Schlenk vessel, we placed a diene solution (83.4 mg, 0.30 mmol) in toluene (1.5 ml), we added camphorosulphonic acid (3.8 mg, 5%moi), and next, the catalyst la (11.9 mg, 5%moi). The vessel contents were mixed at a temperature of 80°C for 53 h The raw post-reaction mixture was analysed using gas chromatography. The conversion was 84%.
Example XI:
Figure imgf000019_0003
In a Schlenk vessel, we placed a diene solution (50.3 mg, 0.30 mmol) in carbon tetrachloride (1.5 ml), and next we added catalyst la (12.2 mg, 5%moi). The vessel contents were mixed at a temperature of 65 °C for 3 h The raw post-reaction mixture was analysed using gas chromatography. The conversion was 100%.
Example XII:
1a 5%mol
. _ , \ ■ ^\ ^- Ph camphorosulp onic acid
AcO-^ OAc + ^ E i: = *. Ac0'
toluene
In a Schlenk vessel, we placed roztwor diacetoxybutenu (1 10.0 mg, 0.64 mmol) and allylbenzene (35.8 mg, 0.30 mmol) in toluene (1.5 ml), we added camphorosulphonic acid (4.7 mg, 7%moi), and next, the catalyst la (12.1 mg, 5%moi). The vessel contents were mixed at a temperature of 80°C for 29 h The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product metathesis was 41%.
Example XIII:
Figure imgf000020_0001
In a Schlenk vessel, we placed an enyne solution (76.1 mg, 0.31 mmol) in toluene (1.5 ml), we added camphorosulphonic acid (4.5 mg, 6%moi), and next, the catalyst la (12.4 mg, 5%moi). The vessel contents were mixed at a temperature of 80°C for 24 h The raw post-reaction mixture was analysed using gas chromatography. The conversion was 100%.
Example XIV:
Figure imgf000020_0002
In a Schlenk vessel, we placed a diene solution (73.5 mg, 0.31 mmol) in methanol (1.5 ml), and next we added catalyst la (1 1.7 mg, 5%moi). The vessel contents were mixed at a temperature of 65°C for 42 h The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product cycloisomerisation was 82%.
Example XV:
Figure imgf000021_0001
In a Schlenk vessel, we placed a diene solution (77.4 mg, 0.31 mmol) in methanol (1.5 ml), and next we added catalyst la (1 1.9 mg, 5%moi). The vessel contents were mixed at a temperature of 65°C for 50 h The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product cycloisomerisation was 88%.
Example XVI:
Figure imgf000021_0002
In a Schlenk vessel, we placed an olefin solution (54.1 mg, 0.25 mmol) in trifluoroethanol (2 ml), and next we added catalyst la (10.8 mg, 5%m0i). The vessel contents were mixed at a temperature of 65 °C for 71 h The raw post-reaction mixture was analysed using gas chromatography. The efficiency of the product isomerisation was 77%.
Example XVII:
Figure imgf000021_0003
In a Schlenk vessel, we placed a norbornene solution (187 mg, 1.4 mmol) in dichloromethane (5 ml) and were mixed at a temperature of 40 °C. Next, we added chlorotrimethylsilane (6.1 mg, 4%moi) and catalyst la (1 1.1 mg, l%moi). The vessel contents were mixed at the same temperature for 10 min, whereafter this was poured into another vessel containing 15 ml of methanol and a white solid was precipitated which was filtered out and dried under reduced pressure over a vacuum pump. We obtained a product (119 mg, 90% efficiency) in the form of a white solid. Example XVIII: Production of polidicyclopentadiene: a flask was loaded with dicyclopentadiene (132 mg, 1.0 mmol) in toluene (5 mL) and mixed at room temperature. Next, we added a chlorotrimethylsilane solution (1.1 mg, l%moi) and catalyst la (0.2 mg, 0.025%moi in toluene and the flask contents were mixed at the same temperature for 10 min. Next, we supplemented the flask with toluene and brought it to boiling temp, in order to wash off the unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure at a temperature of 100 °C for 12 h The conversion of dicyclopentadiene was 99%.
Example XIX:
Figure imgf000022_0001
In a Schlenk vessel, we placed a solution of catalyst la (15.7 mg, 2%moi) in tetrahydrofuran (2.5 ml) and we added sodium hydride (2.8 mg, 7%moi). To this mixture we then added acetophenone (120.3 mg, 1.0 mmol) and isopropyl alcohol (2.5 ml). The vessel contents were mixed at a temperature of 70 °C for 5 h. The raw mixture was purified using column chromatography on a silica gel (elution with cyclohexane: ethyl acetate 20:1). We obtained 95 mg of a liquid product (efficiency 78%).

Claims

Claims
1. A metal complex defined by Formula 1 :
Figure imgf000023_0001
in which:
M denotes ruthenium or osmium;
L and L denote neutral ligands;
X denotes an anionic ligand;
Z denotes a nitrogen atom;
Y denotes an oxygen atom;
R1, R2 denote, independently of one another, a hydrogen atom, a fluoride atom, C1-C25 alkyl, C 1-C25 perfluoroalkyl, C2-C25 alkene, C3-C7 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C1-C25 alkoxyl; C5-C24 aryl, heteroaryl C5-C2o, or a 3-12 membered heterocycle wherein the alkyl groups may be joined together in a ring, preferentially a hydrogen, a nitro group (-N02), a cyanide group (-CN), carboxyl (- COOH), carboxyl (-COOR'), amido (-CONR 2), sulphonyl (-S02R ), formyl (-CHO), sulphonoamido (-S02NR'2), ketone (-COR'), in which R has the following meaning: C]-C5 alkyl, C 1-C5 perfluoroalkyl, C5-C24 aryl;
2. The complex according to Claim 1 , characterised in that the anionic ligand X denotes a fluoride atom, a -CN, -SCN, -OR4, -SR4, -0(C=0)R4, 0(S02)R4, -OSiR3 4, where R4 denotes C,-C12 alkyl, C3-Ci2 cycloalkyl, C2-C,2 alkenyl, or C5 C2o aryl group, which may be substituted with at least one of Ci-Ci2 alkyl, Q-C perhaloalkyl, C1-C12 alkoxyl or a fluoride atom;
R1 denotes a hydrogen atom or methyl group;
R denotes a hydrogen atom; neutral ligands Ll and L2 are selected, independently of one another, from a group
encompassing -P(R5)3, -P(OR5)3 or N-heterocyclic carbene ligands denoted by Formulae 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, 2j, 2k, 21, 2m, 2n, 2o or 2p
Figure imgf000024_0001
Formula 2a Formula 2b Formula 2c Formula 2d
Figure imgf000024_0002
Formula 2e Formula 2f Formula 2g Formula 2h
Figure imgf000024_0003
2p: Formula 2m Formula 2n Formula 2o Formula 2p where:
each R5 denotes, independently of one another, Ct-C12 alkyl, C3-Ci2 cycloalkyl, C5-C2o aryl, 5- 12 membered heteroaryl;
each R 6°, R 7', R 8°, R 9* and R 1'0u denotes, independently of one another, a hydrogen atom, C[-Ci2 alkyl, C3-Ci2 cycloalkyl, C2-Ci2 alkenyl or C5-C2o aryl which may be substituted with at least one Ci-Ci2 alkyl, Cj-Ci2 perhaloalkyl, Cj-Ci2 alkoxyl or fluoride atom, and groups R6, R7, R8, R9 and R10 may possibly be interconnected.
3. The complex according to Claim 1 or 2, characterised in that
X denotes a chlorine atom;
Rl denotes a hydrogen atom or methyl group;
R denotes a hydrogen atom
neutral ligand L1 denotes -P(R5)3 in which substituent R5 has the same meaning as defined above; and
neutral ligand L2 denotes ligands defined by Formula 2a or 2b:
Figure imgf000025_0001
Formula 2a Formula 2g
(
in which substituents R , R , R and R mean as defined above.
4. A method of producing a the ruthenium complex defined in Claim 1, characterised in that the compound defined by Formula 3
Figure imgf000025_0002
Formula 2g in which R1, R2, Z, Υ',Υ2 have meanings as defined above, whereas R3, R13, R14 denote, independently of one another, a hydrogen atom, a fluoride atom, a Ci-C25 alkyl, Ci-C25 perfluoroalkyl, C2-C25 alkene, C3-C7 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C1-C25 alkoxyl, C5-C24 aryl, heteroaryl C5-C20, or a 3-12 membered heterocycle wherein the alkyl groups may be joined together in a ring, preferentially a hydrogen, a nitro group (-N02), a cyanide group (-CN), a carboxyl (-COOH), carboxyl (-COOR'), amido (-CONR 2), sulphonyl (-S02R ), formyl (-CHO), sulphonoamido (- S02NR'2), or ketone (-COR') group, in which R has the following meaning: C 1 -C5 alkyl, Ci- C5 perfluoroalkyl or C5- 4 aryl;
R1 denotes a hydrogen, a fluoride atom, a Ci-C(2 alkyl, C3-C12 cycloalkyl, C2-Ci2 alkenyl, C3- Ci2 cycloalkenyl, C2-Ci2 alkynyl, C3-Ci2 cycloalkynyl, Ci-C l2 alkoxyl, C5- 0 aryl, C5-C20 heteroaryl, or a 3-12 membered heterocycle; is reacted with carbene complexes of ruthenium defined by Formula 4a, 4b, 4c or 4d:
Figure imgf000026_0001
Formula 4a Formula 4b Formula 4c Formula 4d
in which
M denotes ruthenium or osmium;
L , L and L , independently of one another, denote neutral ligands; X and X , independently of one another, denote an anionic ligand; R11 has the same meaning as R1 of Formula 1;
12
R denotes a hydrogen atom, C5-C2o aryl, C5-C2o heteroaryl, vinyl or allenyl.
5. The method according to Claim 4, characterised in that the reaction is carried out over a period from 1 min. to 250 h, at a temperature of from 0 to 150 °C.
6. The method according to Claim 4 or 5, characterised in that the reaction is carried out in a protic or aprotic solvent, a chlorinated solvent or in an aromatic hydrocarbon solvent, or in mixtures thereof.
7. the method according to any of Claim from 4 to 6, characterised in that the reaction is carried out in a solvent selected from among methylene chloride and/or toluene.
8. A use the ruthenium complex defined by Formula 1 defined in Claim 1 , as a (pre)catalyst in metathesis processes, isomerisation and cycloisomerisation of olefins as well as in of the hydrogen transfer reaction.
9. The use according to Claim 8, characterised in that complexes of ruthenium are used as (pre)catalysts in ring closing metathesis reactions, homometatheses, cross-metatheses, "alkene-alkyne" metathesis (ene-yne) or in ROMP polymerisation reactions.
10. The use according to Claim 9, characterised in that complexes of ruthenium are used as (pre)catalysts in a metathetic polymerisation with dicyclopentadiene ring opening.
11. The use according to Claim 8 or 9, characterised in that the reaction is carried out in the presence of an acid or halide derivatives of alkanes and silanes or N-haloimides and amides.
PCT/IB2012/055058 2011-09-26 2012-09-23 Ruthenium or osmium complex, method for its preparation and use thereof Ceased WO2013046108A1 (en)

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