WO2002062809A1 - Complexe de ruthenium et procede de production de compose alcool - Google Patents

Complexe de ruthenium et procede de production de compose alcool Download PDF

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WO2002062809A1
WO2002062809A1 PCT/JP2002/000946 JP0200946W WO02062809A1 WO 2002062809 A1 WO2002062809 A1 WO 2002062809A1 JP 0200946 W JP0200946 W JP 0200946W WO 02062809 A1 WO02062809 A1 WO 02062809A1
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ruthenium complex
compound
ligand
hydrogen
ruthenium
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PCT/JP2002/000946
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Japanese (ja)
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Takeshi Ohkuma
Hiroshi Takeno
Ryoji Noyori
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Nagoya Industrial Science Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
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    • 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
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
    • 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
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5027—Polyphosphines
    • 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
    • B01J2231/60—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
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
    • 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
    • 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
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a novel ruthenium complex and a method for producing an alcohol compound using the same as a catalyst.
  • a ruthenium complex having a phosphine ligand having a polymer-bonded binaphthyl group is a heterogeneous catalyst because the polymer is insoluble, but such a heterogeneous catalyst is generated from the reaction mixture. It can be said that it is easier to separate than homogeneous catalysts.
  • W ⁇ 98Z1222 (Table 2) is a phosphine ligand having a binaphthyl group to which aminomethylpolystyrene is bonded.
  • a heterogeneous R-based catalyst can be said to be advantageous in terms of operation compared to a homogeneous catalyst because the reaction mixture can be filtered and separated. If two catalysts can be reused, it will be more economical than homogeneous catalysts. However, little is known about reusable ruthenium complexes at present.
  • the present invention has been made in view of the above situation, and an object of the present invention is to provide a ruthenium complex that functions as a heterogeneous catalyst for reducing a carbonyl compound and that is excellent in economic efficiency. It is another object to provide a method for producing an alcohol compound using the ruthenium complex. Disclosure of the invention
  • the present inventors have found a compound represented by the general formula (1) as a reusable ruthenium complex that functions as a heterogeneous catalyst for reducing a carbonyl compound.
  • the general formula (1) is not limited to one diastereomer, and may be any of a cis-form and a trans-form.
  • W—PR 3 R 4 where W is a phosphorus atom at the 2- and 2-positions Binaphthyl group may be bonded to the polymer directly or indirectly at any of the 3-8 position and 3′-8 ′ position, and may have a substituent at any other position.
  • R 2 to R 4 may be the same or different and each may be a hydrocarbon group which may have a substituent, and R 1 and R 2 together form a substituent may form a good carbon Kusariwa have a, R 3 and R 4 may form a good carbon Kusariwa have a together a connexion substituent, R 5 ⁇ R 8 may be the same or different, and is a hydrogen atom or a hydrocarbon group which may have a substituent,
  • X and Y may be the same or different, and represent a hydrogen atom, a halogen atom, an alkoxy group, a propyloxyl group or another anion group;
  • Z is a hydrocarbon group which may have a substituent
  • Each ligand of R u can be arranged in any way
  • the ruthenium complex represented by the general formula (1) exhibits almost the same reduction ability as a ruthenium complex (homogeneous catalyst) in which a polymer is not bonded to a pinaphthyl group, that is, the ability to reduce a carbonyl compound to an alcohol compound. I do.
  • a ruthenium complex homogeneous catalyst
  • separation from the reaction mixture is easy, and the operability is superior to that of a homogeneous catalyst.
  • it can be reused multiple times, and in that case, it has almost the same reduction capacity as before reuse.
  • the same substrate can be repeatedly reduced, or different substrates can be sequentially reduced.
  • the polymer represented by W in the general formula (1) is not particularly limited as long as it is a generally known polymer which renders this complex insoluble in a solvent during the reduction reaction of the carbonyl compound.
  • Examples thereof include polyamides and polystyrenes. , Polyethers, polyethylenes, and the like are preferable, and a polystyrene-divinylbenzene copolymer called Merrifield resin, polystyrene, polyamide, aminomethylated polystyrene, diamine resin, Resins and aminomethylated polystyrene are particularly preferred.
  • this polymer is a polymer directly or indirectly bonded to one or both of the 6-position and the 6′-position of the binaphthyl group. It is preferable in that it can be reduced to an alcohol compound in a yield and that the reducing ability does not easily decrease even when reused.
  • the case where the polymer is indirectly linked includes, for example, the case where the polymer is linked via a linear or branched aliphatic hydrocarbon chain, or the case where such an aliphatic hydrocarbon is bonded.
  • Examples include a case where the terminal of the hydrogen is bonded via an ether bond, an ester bond or an amide bond.
  • R 9 is a linear or branched aliphatic hydrocarbon chain which may have a substituent
  • R 1G is a polymer bonded directly or indirectly
  • R 11 is a hydrogen atom or a substituted Examples thereof include a linear or branched aliphatic hydrocarbon chain which may have a group.
  • a preferred example is one (CH 2 ) 3 — CONR 11 — CH 2 — poly (R “is a hydrogen atom or an alkyl group, and poly is polystyrene) bonded to one or both of the 6-position and the 6′-position.
  • the hydrocarbon group which may have a substituent in Ri to R 4 in the general formula (1) is an aliphatic or alicyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group.
  • it may be an araliphatic hydrocarbon or any of these hydrocarbon groups having a substituent, for example, a hydrocarbon group such as alkyl, alkenyl, cycloalkyl, cycloalkenyl, phenyl, naphthyl, and phenylalkyl.
  • a hydrocarbon group such as alkyl, alkenyl, cycloalkyl, cycloalkenyl, phenyl, naphthyl, and phenylalkyl.
  • R 1 and R 2 , and R 3 and R 4 form a ring.
  • R 1 and R 2 , R 3 and R 4 combine to form a carbon chain on which alkyl, alkenyl, cycloalkyl, aryl, alkoxy, ester, acyloxy, and halogen atoms Those having various allowable substituents such as, nitro and cyano groups may be selected.
  • the amine ligand in the general formula (1) includes ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 2,3-diaminobutane , 1,2-cyclopentadiamine, 1,2-cyclohexanediamine, N-methylethylenediamine, N, N'-dimethylethylenediamine, N, N, ⁇ 'trimethylethylenediamine, ⁇ , ⁇ , N' , N'-tetramethylethylenediamine, ⁇ -phenylenediamine, ⁇ -phenylenediamine and the like.
  • an optically active diamine compound can also be used.
  • optically active 1,2-diphenylethylenediamine, 1,2-cyclohexanediamine, 1,2-cycloheptandiamine, 2,3-dimethylbutanediamine, monomethyl-2,2-diphenylethylenediamine, 1-isobutyl-2,2-diphenylethylenediamine, 1-isopropyl-2,2-diphenylethylenediamine, 1-methyl-2,2-di ( ⁇ -methoxyphenyl) ethylenediamine, 1-isobutyl1-2,2 —Di ( ⁇ -methoxyphenyl) ethylenediamine, 1-isopropyl-12,2-di ( ⁇ -methoxyphenyl) ethylenediamine, 1-benzyl-2,2-di ( ⁇ -methoxyphenyl) ethylenediamine, 1-methyl -2,2-Dinaphthylethylenediamine, 1-isobutyl-2,2-dimine, 1-isopropyl-1,2,2-dinaphthylene, Ru can be
  • the synthesis of the ruthenium complex represented by the general formula (1) is achieved by reacting the phosphine ligand and the amine ligand in this order with ⁇ ⁇ or in reverse order, or simultaneously, with the ruthenium complex as the raw material. Can be synthesized.
  • the phosphine ligand for example, a phosphine ligand described in WO 98/122202 (Table 2) may be used. Specific synthesis of the ruthenium complex represented by the general formula (1) is described in, for example,
  • the procedure can be performed according to the procedure described in Japanese Patent Application Laid-Open No. 11-189600, and an outline of the procedure will be described below.
  • ruthenium complex As the ruthenium complex as a starting material for complex synthesis, zero-valent, monovalent, divalent, trivalent, and even higher-valent complexes can be used. When a zero-valent or monovalent ruthenium complex is used, ruthenium must be oxidized by the final stage. When a divalent complex is used, it can be synthesized by reacting a ruthenium complex with a phosphine ligand and an amine ligand sequentially or in reverse order, or simultaneously. If a trivalent or tetravalent or higher ruthenium complex is used as a starting material, it is necessary to reduce ruthenium atoms by the final stage.
  • ruthenium complex to be used as a starting material for example, those described in JP-A-11-189600 can be used, but ruthenium chloride ( ⁇ ) ) Hydrate, ruthenium bromide (II) hydrate, ruthenium iodide (m) hydrate, etc., inorganic ruthenium compounds, [ruthenium dichloride (norbornadiene)] polynuclear, [ruthenium dichloride (cyclo Kutagen)] Multinuclear, bis (methylali) Ru) Ruthenium compound coordinated with a gen such as ruthenium) cyclooctadiene, etc., [ruthenium dichloride (benzene)] binuclear, [ruthenium dichloride (p-cymene)] binuclear, [2 Ruthenium complexes coordinated with aromatic compounds such as ruthenium chloride (trimethylbenzene)] binuclear, [ruthenium dichloride (hexamethylbenzen
  • the reaction between the ruthenium complex, which is the starting material, and the phosphine ligand is carried out in an aromatic hydrocarbon solvent such as toluene or xylene, an aliphatic hydrocarbon solvent such as pentane or hexane, or a halogen-containing hydrocarbon solvent such as methylene chloride.
  • aromatic hydrocarbon solvent such as toluene or xylene
  • aliphatic hydrocarbon solvent such as pentane or hexane
  • a halogen-containing hydrocarbon solvent such as methylene chloride.
  • Ether solvents such as ether and tetrahydrofuran
  • alcohol solvents such as methanol, ethanol, 21-propanol, butanol, and benzyl alcohol
  • acetonitrile N, N-dimethylacetamide (DMA)
  • organic solvents containing heteroatoms such as N, N-dimethylformamide (DMF), N-methylvinylidone and dimethylsulfoxide (DMSO)
  • the reaction temperature is between 100 ° C and 200 ° C.
  • the phosphine-ruthenium halide complex can be obtained.
  • the phosphine ligand Since the phosphine ligand has a R 1 and is in a solid state (for example, a bead shape) and may be destroyed by stirring during the reaction, the reaction must be performed in a stationary state. Is preferred. In this case, a longer reaction time is required as compared with the case where the reaction is performed while stirring in a homogeneous system using a phosphine ligand not bonded to the polymer.
  • the reaction between the obtained phosphine ruthenium halide complex and the amine ligand is carried out in an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as pentane and hexane, and a solvent such as methylene chloride. Hydrocarbon solvents, ether solvents such as ether, tetrahydrofuran, etc. Reaction temperature in alcoholic solvents such as ethanol, ethanol, 2-propanol, butanol, and benzyl alcohol; organic solvents containing heteroatoms such as acetonitrile, DMA, DMF, N-methylpyrrolidone, and DMS ⁇ The reaction is carried out at a temperature of from 100 ° C.
  • the diamine-phosphine-ruthenium halide complex can be obtained by hydrogenating the obtained diamine-phosphine-ruthenium halide complex under hydrogen transfer or hydrogen transfer-type reduction reaction conditions.
  • a diamine-phosphine ruthenium halide complex can be converted to an aromatic hydrocarbon solvent such as toluene or xylene, an aliphatic hydrocarbon solvent such as pentane or hexane, a halogen-containing hydrocarbon solvent such as methylene chloride, ether, or tetrahydrofuran.
  • Ether solvents such as methanol, ethanol, 2-propanol, butanol, benzyl alcohol, etc.
  • organic solvents containing heteroatoms such as acetonitrile, DMA, DMF, N-methylpyrrolidone, DMS O, etc.
  • a diamine-phosphine ruthenium hydride complex can be obtained. Also, first, the phosphine-ruthenium halide complex can be converted to a phosphinruthenium hydride complex, and then reacted with diamine to obtain a diamine-phosphine-ruthenium halide complex.
  • the amount used depends on the reaction vessel and economy, but the molar ratio with the carbonyl compound as the reaction substrate SZC (S is the substrate, C Is a catalyst) can be used in the range of 100 to 100 000 000, and in consideration of reuse, it is preferably used in the range of 500 to 100 000, It is particularly preferable to use in the range of 00. It is desirable to add a base to the ruthenium complex represented by the general formula (1) regardless of what X and Y are.
  • the carbonyl compound can be prepared by mixing with a sulfonyl compound in the presence of a base and then applying hydrogen pressure or stirring in the presence of a hydrogen donor. It is also effective to carry out hydrogenation.
  • the amount of the base to be added is 0.5 to 100 000 equivalents, preferably 0.5 to 200 equivalents, particularly preferably 2 to 10 equivalents, based on the ruthenium complex represented by the general formula (1). It is 0 equivalent.
  • the base is not limited as long as it generates a diamine-phosphine ruthenium hydride, and examples thereof include metal hydrides such as hydrogen, sodium borohydride, and lithium aluminum hydride, nesium, and methyllithium. Organic metal compounds such as ethyl lithium, propyl lithium and the like can also be used.
  • any solvent can be used as long as it dissolves a reaction substrate and makes the catalyst a heterogeneous system. Can be used.
  • aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as pentane and hexane, octane-containing hydrocarbon solvents such as methylene chloride, ether solvents such as ether and tetrahydrofuran, and methanol , Ethanol, 2-propanol, butanol, benzyl alcohol and other alcoholic solvents, acetonitrile, DMA, DMF, N-methylpyrrolidone, DMS O and other organic solvents containing heteroatoms, and any combination of these A mixed solvent or the like can be used.
  • the reaction solvent is preferably an alcoholic solvent, and among them, 2-propanol is particularly preferable.
  • the ruthenium complex represented by the general formula (1) is a heterogeneous catalyst and is insoluble in the reaction solvent. Therefore, in order to promote the reduction reaction, the presence of a polar solvent that swells the ruthenium complex is required. preferable.
  • a polar solvent for example, THF, DMA, DMF, DMSO and the like are preferable, and among them, DMF is particularly preferable.
  • the pressure of hydrogen in this reduction reaction is 0.5 atm, which is sufficient because the present catalyst system is extremely active. However, in consideration of economy, the pressure is in the range of 1 to 200 atm, preferably 3 to 10 atm. A range of 0 atm is desirable, but high activity can be maintained even at 50 atm or less in consideration of the economics of the entire process.
  • the reaction temperature is preferably from 15 ° C to 100 ° C in consideration of economy, but the reaction can be carried out at around room temperature of 25 to 40. You. However, this reduction reaction is characterized in that the reaction proceeds even at a low temperature of 130 to 0 ° C.
  • the reaction time varies depending on the reaction conditions such as the concentration of the reaction substrate, temperature, and pressure, but the reaction is completed in several minutes to several days.
  • the hydrogenation reaction of the carbonyl compound in this reduction reaction can be carried out either in a batch system or in a continuous system.
  • the asymmetric carbonyl compound is reduced in the reaction solvent in the presence of hydrogen or a compound that donates hydrogen to form an optical system.
  • Active alcohol compounds can be produced with high selectivity.
  • the amine ligand is preferably an optically active diamine.
  • the chiral center carbon of the amine ligand may be R, R-form, S, S-form, or a mixture of both (for example, racemic form). , R body or S, S body.
  • R, R or S, S isomer of the amine ligand it is preferable to decide whether to use the R, R or S, S isomer of the amine ligand according to the type of the asymmetric carbonyl compound as the reaction substrate. In other words, depending on the type of the asymmetric carbonyl compound, better results are obtained when the amine ligand is R or R, or better results when the amine ligand is S or S. Therefore, it is preferable to determine the steric structure of the amine ligand according to the reaction substrate. These ruthenium complexes are preferable because the reducing ability of the heterogeneous catalyst is maintained with almost no deterioration even when reused a plurality of times.
  • the amine ligand is preferably an optically active diamine.
  • the chiral center carbon of the amine ligand may be an R, R form, an S, S form, Both may be present in a mixture (for example, a racemic form), but it is preferable that the R and R forms or any of the S and S forms.
  • the phosphine ligand may be an R-form, an S-form, or a mixture of both (for example, a racemic form). Preferably, there is. Whether the phosphine ligand is of the R-form or of the S-form is preferably determined according to the type of the asymmetric carbonyl compound as the reaction substrate.
  • an asymmetric carbonyl compound can be produced in a reaction solvent in the presence of hydrogen or a compound donating hydrogen.
  • Reduced optically active alcohol Compounds can be produced with high selectivity.
  • the phosphine ligand may be an R-form, an S-form, or a mixture of both (for example, a racemic form). It is preferable that there is. Whether the phosphine ligand is of the R-form or of the S-form is preferably determined according to the type of the asymmetric carbonyl compound as the reaction substrate.
  • the asymmetric carbonyl compound which is a reaction substrate for obtaining an optically active alcohol compound with high selectivity is not particularly limited.
  • ruthenium complex represented by the general formula (1) a mixture of (R, RR) and (R, SS) in a one-to-one relationship is used to form an asymmetric carbonyl having an aromatic hydrocarbon bonded to a carbonyl carbon.
  • an optically active alcohol compound having the same steric structure as that obtained when the (R, RR) form is used can be obtained with high selectivity. This is because the (R, RR) body is It is presumed that the reaction speed is higher than that of the (R, SS) body.
  • FIG. 1 is an explanatory diagram showing starting materials used for synthesis of a polymer-bound ruthenium complex
  • FIG. 2 is an explanatory diagram showing the hydrogenation reaction of 1'-acetonaphthone
  • FIG. 3 is an explanatory diagram showing a hydrogenation reaction of an aromatic ketone
  • FIG. 4 is an explanatory diagram showing the hydrogenation reaction of 0-honone
  • FIG. 5 is an explanatory diagram showing the hydrogenation reaction of 2,4,4-trimethyl-2-cyclohexanone.
  • APBB I NAP 2,2'-bis (diphenylphosphino) with aminomethyl polymer bound at the 6-position — 1, 1, —binaphthyl
  • APBB I NAP propylaminomethyl polymer is bound at the 6-position
  • 2 '—bis (diphenylphosphino) — 1, 1, -binaphthyl is abbreviated as ⁇ ⁇ ⁇ ⁇
  • 1,2,2-diphenylethylenediamine is abbreviated as “DP EN”.
  • APBB I NAP” and “PBB INAP” were provided by Oxford Asymm etry International.
  • the R, RR—polymer-bound ruthenium complex of interest is washed by washing with ether (5. OmL) seven times, and then dried under reduced pressure (1 Torr) for 24 hours at 40 ⁇ (Fig. 1). (See 0.3 24 mm o 1 / g, 340. l mg, 0.110 mm o 1). The purity of the complex by 31 P-NMR was 81%.
  • Example 3 Synthesis of R, RR / SS-polymer-bound ruthenium complex (R, R)-Same as Example 1 except that racemic (Earth) -DPEN was used instead of DPEN.
  • R, RRZS S—polymer single bond type ruthenium complex that is, a one-to-one mixture of (R, RR) form and (R, SS) form was obtained.
  • Example 5 Asymmetric hydrogenation reaction of aromatic ketones (see Fig. 2) In a 500 mL glass autoclave equipped with a Teflon-coated magnetic stir bar, the R, obtained in Example 1, was added. RR—polymer-bound ruthenium complex (29.3 mg, catalyst content 9.48 / imo 1) The air in the autoclave was replaced with argon. In this autoclave, 1'-acetonaphthone (20.1 g, 118 mmo) in a 1: 1 mixture (1-20 mL) of 2-propanol and DMF, which had been degassed by argon publishing, was added.
  • Example 7 Continuous asymmetric hydrogenation reaction of aromatic ketones (see Fig. 3) Using the R, RR-polymer one-bonded ruthenium complex obtained in Example 1,
  • the catalyst was reused in the same manner as in Example 5 above, and the hydrogenation reaction of 0-nonone was repeatedly performed.
  • the results are shown in Table 3 below. As is evident from Table 3, the conversion and the enantioselectivity remained high after the end of the first experiment.
  • the total TON was 29, 260.
  • the catalyst was reused in the same manner as in Example 5 above, and the hydrogenation reaction of 2,4,4-trimethyl-12-cyclohexanone was repeated.
  • the results are shown in Table 4 below. As is evident from Table 4, the conversion and enantio selectivity remained high after the ninth experiment was completed.
  • the total TON was 27,250.
  • the method for producing a ruthenium complex and an alcohol of the present invention can be used to obtain useful optically active alcohols in synthetic intermediates of various medicines and agricultural chemicals and various functional materials.

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Abstract

L"invention concerne un complexe de ruthénium fonctionnant comme un catalyseur pour la catalyse hétérogène, représenté par des complexes de (R,RR)-ruthénium du type à liaison polymère. Ce complexe est presque égal aux complexes comportant un groupe binaphtyle non lié à un polymère (catalyseurs pour catalyse homogène) dans son pouvoir de réduction, c"est à dire de réduire des composés carbonyles en composés alcools. Puisque le complexe de ruthénium est un catalyseur de catalyse hétérogène, il peut être facilement séparé du milieu réactionnel, et il est supérieur, en efficacité opératoire, aux catalyseurs de catalyse homogène. Après séparation et récupération, le complexe de ruthénium peut être réutilisé une ou plusieurs fois. A la réutilisation, le complexe de ruthénium montre presque le même pouvoir de réduction que lors de la première utilisation, et il peut être utilisé pour réduire le même substrat ou afin de réduire successivement différents substrats.
PCT/JP2002/000946 2001-02-06 2002-02-06 Complexe de ruthenium et procede de production de compose alcool WO2002062809A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7164026B2 (en) 2002-11-15 2007-01-16 Takasago International Corporation Polymer-carrying optically active binaphthyl type oxazoline compound
JP2010260969A (ja) * 2009-05-08 2010-11-18 Nagoya Univ 高分子配位子、アルミニウム錯体及びポリラクチドの製造方法
JP2015502329A (ja) * 2011-10-06 2015-01-22 フイルメニツヒ ソシエテ アノニムＦｉｒｍｅｎｉｃｈ Ｓａ Ｒｕ／二座配位子錯体によるアルデヒドの選択的水素化
JP2016532545A (ja) * 2013-08-02 2016-10-20 ザ・ガバナーズ・オブ・ザ・ユニバーシティー・オブ・アルバータ 連続流通式反応装置で使用するための触媒系ならびにその製造および使用方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7164026B2 (en) 2002-11-15 2007-01-16 Takasago International Corporation Polymer-carrying optically active binaphthyl type oxazoline compound
JP2010260969A (ja) * 2009-05-08 2010-11-18 Nagoya Univ 高分子配位子、アルミニウム錯体及びポリラクチドの製造方法
JP2015502329A (ja) * 2011-10-06 2015-01-22 フイルメニツヒ ソシエテ アノニムＦｉｒｍｅｎｉｃｈ Ｓａ Ｒｕ／二座配位子錯体によるアルデヒドの選択的水素化
JP2016532545A (ja) * 2013-08-02 2016-10-20 ザ・ガバナーズ・オブ・ザ・ユニバーシティー・オブ・アルバータ 連続流通式反応装置で使用するための触媒系ならびにその製造および使用方法

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