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WO2006137165A1 - Catalyseur d'hydrogenation et procede de fabrication d'un alcool utilisant ce catalyseur - Google Patents

Catalyseur d'hydrogenation et procede de fabrication d'un alcool utilisant ce catalyseur Download PDF

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WO2006137165A1
WO2006137165A1 PCT/JP2005/011674 JP2005011674W WO2006137165A1 WO 2006137165 A1 WO2006137165 A1 WO 2006137165A1 JP 2005011674 W JP2005011674 W JP 2005011674W WO 2006137165 A1 WO2006137165 A1 WO 2006137165A1
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group
general formula
hydrogenation catalyst
compound
reaction
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PCT/JP2005/011674
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English (en)
Japanese (ja)
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Noriyuki Utsumi
Kunihiko Murata
Kunihiko Tsutsumi
Takeaki Katayama
Takeshi Ohkuma
Ryoji Noyori
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Kanto Kagaku Kabushiki Kaisha
Nagoya Industrial Science Research Institute
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Priority to PCT/JP2005/011674 priority Critical patent/WO2006137165A1/fr
Publication of WO2006137165A1 publication Critical patent/WO2006137165A1/fr

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    • 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
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • B01J2531/80—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

Definitions

  • the present invention relates to a novel hydrogenation catalyst and a method for producing an alcohol compound using the same.
  • the yield and enantiomeric excess may be low depending on the reaction substrate, and the structure of the applicable cane compound was limited.
  • the present invention has been made to solve such problems, and provides a hydrogenation catalyst useful in producing an alcohol compound that has been difficult to obtain so far, and an alcohol using the hydrogenation catalyst. It aims at providing the manufacturing method of a compound.
  • Lewis acid acts on a Group 8 or Group 9 transition metal complex having a metal amide bond, thereby producing hydrogen.
  • a new catalyst with activation ability could be obtained.
  • a new catalyst capable of activating hydrogen can be obtained by reacting Lewis acid with a Group 8 or Group 9 transition metal complex having an amine ligand.
  • Lewis acid is used in the sense of a compound that accepts electrons, and does not include a prested acid that releases protons.
  • the hydrogenation catalyst of the present invention has a group 8 or 9 having a metal amide bond.
  • Group transition metal complexes and Lewis acids excluding Brenstead acid that releases protons, the same shall apply hereinafter
  • group 8 or group 9 transition metal complexes having metal amide bonds and Lewis acids It was obtained by mixing.
  • a group 8 or group 9 transition metal complex having an amine ligand and a Lewis acid are included, or a group 8 or group 9 transition metal complex having an amine ligand and a Lewis acid are mixed in advance. It was obtained by this.
  • the method for producing an alcohol compound of the present invention is to obtain an alcohol compound by hydrogenating a ketone compound with such a hydrogenation catalyst. If the hydrogenation catalyst of the present invention is used, an alcohol compound that has been difficult to obtain can be produced.
  • the group 8 or group 9 transition metal complex having a metal amide bond is preferably a compound represented by the following general formula (1).
  • the metal amide bond in the general formula (1) means a bond between M and NR 4 metal and nitrogen.
  • the group 8 or group 9 transition metal complex having an amine ligand is preferably a compound represented by the following general formula (2).
  • the amine ligand of the general formula (2) means a coordinate bond between the metal of NHR 4 and nitrogen in X ⁇ .
  • R 1 and R 2 may be the same or different from each other, and may have a substituent, an alkyl group, a phenyl group, A group, a naphthyl group or a cycloalkyl group, or a part of the ring when bonded to each other to form an alicyclic ring,
  • R 3 is an alkyl group, a naphthyl group, a phenyl group, or camphor, which may have a substituent,
  • R 4 is a hydrogen atom or an alkyl group
  • Ar is an optionally substituted benzene or an optionally substituted pentagen group bonded to M 1 via a ⁇ bond.
  • M 1 is ruthenium, rhodium or iridium
  • R 1 and R 2 in the general formula (1) and the general formula (2) are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl And an alkyl group having 1 to 10 carbon atoms such as a group.
  • phenyl groups having 1 to 5 carbon atoms such as phenyl groups, 4-methylphenyl groups, 3,5-dimethylphenyl groups, halogen substitutions such as 4-fluorophenyl groups and 4-chlorophenyl groups
  • a phenyl group having an alkoxy group such as a 4-methoxyphenyl group.
  • naphthyl group, 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro-2-na Examples include a butyl group.
  • a cyclopentyl group, a cyclohexyl group, etc. are mentioned.
  • R 1 and R 2 are also mentioned alicyclic ring having an unsubstituted or substituted group to form a ring, cyclopentane ring, for example the R 1 and R 2 to form a ring Examples include N-cyclohexane ring.
  • R 1 and R 2 are phenyl groups, or a cyclohexane ring in which R 1 and R 2 are combined to form a ring.
  • the alkyl group at R 3 in (2) is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, etc.
  • These alkyl groups may have a substituent, for example, may have one or more fluorine atoms as a substituent.
  • alkyl group containing one or more fluorine atoms examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group.
  • the naphthyl group which may have a substituent include, for example, an unsubstituted naphthyl group, a 5,6,7,8-tetrahydrone-1-naphthyl group, and a 5,6,7,8-tetrahydro-2. -Naphthyl group and the like.
  • Examples of the optionally substituted phenyl group include unsubstituted phenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2,4 , 6- ⁇ Phenyl group having an alkyl group such as triisopropylphenyl group, 4-fluorophenyl group, phenyl group having a halogen substituent such as 4-chlorophenyl group, alkoxy such as 4-methoxyphenyl group And a phenyl group having a group.
  • R 4 in general formula (1) and general formula (2) include alkyl groups having 1 to 5 carbon atoms such as a methyl group and an ethyl group, and a hydrogen atom. Preferred is hydrogen.
  • Ar in general formula (1) and general formula (2) includes, for example, unsubstituted benzene, toluene, o-, m-, and P-xylene, o-, m-, and P-cymene. 1, 2, 3-, 1, 2, 4-, and 1, 3, 5, 5-trimethylbenzene, 1, 2, 4, 5-tetramethylbenzene, 1, 2, 3, 4-tetramethylbenzene And benzene having an alkyl group, such as Penyu-Methylbenzene and Hexamethylbenzene.
  • the cyclopentenyl group which may have a substituent includes a cyclopentaenyl group, a methylcyclopentenyl group, a 1,2-dimethylcyclopentenyl group, a 1,3-dimethylcyclopentenyl group, 1,2,3-trimethylcyclopentenyl group, 1,2,4trimethylcyclopentenyl group, 1,2,3,4-tetramethylcyclopentenyl group, and 1,2,3, Examples include 4,5-pentamethylcyclopentagenyl group.
  • M 1 in general formula (1) and general formula (2) is a transition element of group 8 or group 9, among which ruthenium, rhodium and iridium are preferred.
  • X 1 in general formula (2) is anionic.
  • Porate group acetooxy group, benzoyloxy group, (2, 6-dihydroxybenzoyl) oxy group, (2, 5-dihydroxybenzoyl) oxy group, (3-aminobenzoyl) oxy group, (2, 6 -Methoxybenzoyl) oxy group, (2,4,6-triisopropylbenzoyl) oxy group, 1-naphthalenecarboxylic acid group, 2-naphthalenecarboxylic
  • the compounds represented by the general formula (1) and the general formula (2) can be regarded as a structure in which a bidentate ethylenediamine compound (RSSO sNH CHR ⁇ CHR SN HR 4 ) is bonded to a metal.
  • a bidentate ethylenediamine compound RSSO sNH CHR ⁇ CHR SN HR 4
  • specific examples of the ethylenediamine compound are listed as follows.
  • M 2 is boron, aluminum, Keimoto scandia Jiumu, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, said thorium, Jirukoniu arm , Niobium, molybdenum, technetium, ruthenium, rhodium, paradium, silver, cadmium, indium, tin, antimony, lanthanum, cerium, prasedium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, dysprosium Ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth or actinoide
  • m is an integer of 1 or 2
  • X 2 is an anionic group, an alkyl group, or an optionally substituted phenyl group, which may be the same or different from each other, and n represents an integer of 2 to 14.
  • —M 2 in general formula (3) includes aluminum, boron, silicon, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, and zirconium.
  • X 2 in the general formula (3) may be the same or different from each other, and may be an anionic group, an alkyl group, or a phenyl group which may have a substituent, and n is 2-1 Indicates an integer of 4.
  • Specific examples of X 2 include chlorine group, bromine group, iodine group, triflate group, hydroxyl group, nitro group and sulfate group. Preferred are a chlorine group, a bromine group, an iodine group, and a triflate group, and most preferred is a triflate group.
  • Specific examples of the compound represented by the general formula (3) include scandium chloride, yttrium chloride, lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, samarium chloride, plutonium chloride, gadolinium chloride, holmium chloride, Ytterbium chloride, aluminum chloride, scandium bromide, yttrium bromide, lanthanum bromide, cerium bromide, praseodymium bromide, neodymium bromide, samarium bromide, plutonium bromide, gadolinium bromide, holmium bromide Ytterbium bromide, aluminum bromide, scandium iodide, yttrium iodide, lanthanum iodide, cerium iodide, praseodymium iodide, neodymium iodide,
  • a catalyst containing a group 8 or group 9 transition metal complex having a metal amide bond and a Lewis acid, or a group 8 or group 9 transition metal complex having an amine ligand is used. It is presumed that the actual hydrogenation catalyst will be generated in the hydrogenation reaction system when using a catalyst containing Lewis acid. That is, before carrying out the hydrogenation reaction, a group 8 or group 9 transition metal complex having a metal amide bond or an amine ligand, a reaction substrate, a Lewis acid, and a hydrogenation reaction solvent are added to a pressure resistant reaction vessel. The hydrogenation reaction is then carried out by stirring in the presence of hydrogen or a compound that donates hydrogen.
  • a group 8 or group 9 transition metal complex having a metal amide bond and a Lewis acid mixed in advance, or a group 8 or group 9 transition having an amine ligand are used.
  • a mixture of a metal complex and a Lewis acid in advance first prepare a hydrogenation catalyst by adding the metal complex, Lewis acid and reaction solvent and stirring, and prepare the prepared hydrogenation catalyst and reaction.
  • the hydrogenation reaction is performed by adding the substrate and the hydrogenation reaction solvent to the pressure-resistant reaction vessel, and then stirring in the presence of hydrogen or a compound that donates hydrogen.
  • a solvent used for preparing the catalyst a protic solvent to an aprotic solvent can be used.
  • methanol, ethanol, 2-propanol, water, toluene, tetrahydrofuran, acetone, and N, N-dimethylformamide is used.
  • the use of a protic solvent is preferable, and methanol and ethanol are more preferable.
  • the reaction time is not particularly limited, and the reaction is often completed within a few minutes to an hour at room temperature.
  • Group 8 or 9 transition metal complexes with metal amide bonds or amine coordination The amount of Lewis acid used for a group 8 or 9 transition metal complex with a ligand varies depending on the concentration of the hydrogenation reaction to be performed and the substrate-catalyst ratio, but is generally from 0.1 to 10 molar equivalents. It is.
  • a method for preparing a compound represented by the general formula (1) which is an example of a group 8 or group 9 transition metal complex having a metal amide bond, is described in Angew. Chem., Int. Ed. Engl. Vol. 36, p285 (1997) and J. Org. Chem. Vol. 64, P 2 186 (1999).
  • a transition metal complex such as a ruthenium allene complex, a pentamethylcyclopentagenyl rhodium complex, or a pentamethylcyclopentadiene dilysium complex and a sulfonyldiamine ligand in the presence of an excessive strong base such as KOH. It can be synthesized by reacting.
  • transition metal complexes such as ruthenium allene complex, pentamethylcyclopentanegenyl rhodium complex, pentamethylcyclopentanegenyl iridium complex, and sulfonyldiamine ligands, and weak bases such as triethylamine are present. It can be synthesized by reacting below. It can also be synthesized by the reaction of a metal amide complex having a sulfodilamine ligand and hydrogen chloride.
  • an alcohol compound is obtained by hydrogenating a cane compound with the hydrogenation catalyst of the present invention described above in the presence of hydrogen or a compound that donates hydrogen.
  • a hydrogenation catalyst and a cane compound are placed in a solvent, mixed in the presence of hydrogen or a compound that donates hydrogen, and the cane compound is hydrogenated to obtain an alcohol compound.
  • the amount of catalyst used at this time is the amount of the ketone compound relative to the metal complex.
  • S / C is expressed as S / C (S is a substrate, C is a catalyst)
  • SZC is not particularly limited, but considering practicality, it should be used in the range of 10 to 100, 0 0 0 It is preferable to use in the range of 5 0 to 1 0, 0 0 0.
  • the hydrogenation reaction solvent include alcohol solvents such as methanol, ethanol, 2-propanol, 2-methyl-2-propanol, 2-methyl-2-butanol, tetrahydrofuran (THF), and jetyl ether.
  • Ether solvents such as DMSO, DMF, and acetonitrile, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as pentane and hexane, halogen-containing hydrocarbons such as methylene chloride
  • a solvent, water or the like can be used alone or in combination.
  • a mixed solvent of the solvent exemplified above and other solvents can also be used.
  • alcohol-based solvents are preferable, and methanol and ethanol are more preferable in order to proceed the reaction efficiently.
  • the amount of the solvent is determined by the solubility and economics of the reaction substrate.
  • the concentration of the hydrogenation reaction is from a low concentration of 1% by weight or less to 99% by weight or more of almost no solvent.
  • the reaction can be carried out in the state, and the reaction is preferably carried out at a concentration of 5 to 80% by weight. Under these high concentration conditions, few examples of hydrogenation reactions proceeding with high reactivity are known, and it is possible to increase the production amount per batch of the hydrogenation reaction. Very advantageous.
  • the hydrogen pressure is not particularly limited, but can be carried out in the range of 1 to 200 atm. In view of economy, the range of 5 to 150 atm is preferable.
  • the reaction temperature is not particularly limited, but in consideration of economy, it can be carried out in the range of 150 to 100 ° C, preferably in the range of 30 to 60, More preferably, it is carried out in the range of 60 ° C.
  • the reaction time depends on the reaction conditions such as the type of reaction substrate, concentration, szc, temperature, and pressure, and the type of catalyst. Therefore, various conditions may be set so that the reaction is completed within a few minutes to several days, and it is particularly preferable to set the conditions so that the reaction is completed within 5 to 24 hours. Further, the reaction product can be purified by a known method such as column chromatography, distillation, recrystallization and the like.
  • a base it is not essential to add a base to the reaction system, so that the hydrogenation reaction of the ketone compound proceeds rapidly without adding a base.
  • the addition of a base is not excluded.
  • a small amount of a base may be optionally added depending on the structure of the reaction substrate and the purity of the reagent used.
  • the two asymmetric carbons in the compounds represented by the general formulas (1) and (2) are both in the (R) form in order to obtain an optically active alcohol compound. Or both must be in (S) form.
  • an optically active alcohol having a desired absolute configuration can be obtained with high selectivity.
  • both of these chiral carbons do not need to be in the (R) form or (S) form, and may be either independently.
  • the ketone compound is hydrogenated without adding a base.
  • the corresponding optically active alcohol compound can be obtained by hydrogenation. Therefore, according to the method for producing an alcohol compound of the present invention, it can be applied to a ketone compound having a wider structure as compared with a conventionally known method using a hydrogenation catalyst not containing a base. The reaction is not affected by impurities and proceeds with good reproducibility, and the target substance can be obtained with high optical purity and high yield.
  • the hydrogenation catalyst of the present invention for example, conventional hydrogen Hydrogenate cyclic ketones that could not be reduced efficiently with a fluorination catalyst to produce optically active cyclic alcohols, or ketones having an olefin moiety or an acetylene moiety (especially ⁇ , / 3-bonds are olefin moieties or Hydrogenation of an acetylene moiety (ketone) to produce an optically active alcohol having an olefin moiety or an acetylene moiety, a hydrogenated ketone having a hydroxyl group to produce an optically active alcohol having a hydroxyl group, or a halogen substituent.
  • ketones having an olefin moiety or an acetylene moiety especially ⁇ , / 3-bonds are olefin moieties or Hydrogenation of an acetylene moiety (ketone) to produce an optically active alcohol having an olefin moiety or an acetylene moiety, a hydrogenated
  • Hydrogenated ketones especially ketones having an eight-rogen substituent at the ⁇ -position
  • Hydrogenated ketones to produce optically active alcohols having halogen substituents
  • hydrogenated chromanone derivatives to produce optically active chromanols
  • hydrogenated diketones To produce optically active diols or hydrogenate ketoesters to produce optically active diols.
  • the optically active hydroxyamide can be produced by producing an active hydroxy ester or by hydrolyzing ketoamide, and the method described in the present invention is extremely useful.
  • Typical examples of ketone compounds applicable to the process for producing the optically active alcohol of the present invention are listed below.
  • the hydrogenation reaction of a ketone compound in the present invention can be performed in a batch type. It can also be implemented in a continuous mode.
  • GC gas chromatography
  • HPLC high performance liquid chromatography
  • R u [(S, S) -T sdpen] (p-c ym ene) was synthesized according to the technique described in the above-mentioned publicly known literature, and the specific procedure is shown below. First, in a Schlenk-type reaction tube purged with argon, [Ru C 1 2 (p-c ym ene)] 2 (3 10 mg, 0.5 mmol), S, S)-T s DP EN (3 70 mg, 1 mm o 1), KOH (400 mg, 7 mm o 1), and methylene chloride 7 m 1 were charged.
  • Example 2-4 The reaction was carried out under the same conditions as in Example 1 except that the amount of Y b (OT f) 3 was changed to synthesize (R) -2-2-chloro-1-phenylethanol. The results are summarized in Table 1. Thus, a wide range of molar equivalents of Y b (OT f) 3 can be used for ruthenium.
  • Example 5 The reaction was carried out under the same conditions as in Example 1 except that S c (OT f) 3 or BF 3 '0 (C 2 H 5 ) 2 was used instead of Y b (OT f) 3 , and (R )-2-Chromium-1-Phenylethanol was synthesized.
  • Table 2 As described above, various types of Lewis acid used in combination with the metal complex can be used.
  • RuCl [(S, S)-T sdpen] (mesitylene) (1. 2 4 mg, 2 mo 1), Y b ( ⁇ T f) 3 (1. 2 4 mg, 2 mo 1),-chloroacetophe Non (0.3 g, 2 mm o 1) was charged and replaced with argon. After adding 4 ml of methanol and pressurizing with hydrogen, it was replaced 10 times. Hydrogen was charged up to 20 atm to start the reaction. After stirring at 30 ° C for 15 hours, the reaction pressure was returned to normal pressure. From 1 HNMR and GC analysis of the product, 9 7% ee (R) -2-black-1 -phenylethanol was produced in 89% yield.
  • a hydrogenation catalyst consisting of a chloride complex and Y b (OT f) 3 is also useful for the asymmetric hydrogenation of hypochloroacetophenone.
  • RuCl [(S, S) -Tsdpen] (mesitylene) was synthesized according to the method described in the above-mentioned publicly known document, and a specific procedure is shown below. First, in a Schlenk-type reaction tube purged with argon, [R u C l 2 (mesitylene)] 2 (1.5 g, 2.5 mm o 1), (S, S)-T s DP EN U.
  • a stainless steel clave was charged with the catalyst prepared in Example 36 (2.5 mg) and 4-chromanone (0.3 g, 2 mm o 1), and substituted with argon. Methanol 2 m 1 was added, pressurized with hydrogen, and then replaced 10 times. Hydrogen was charged to 30 atm to start the reaction. After stirring at 50 ° C. for 15 hours, the reaction pressure was returned to normal pressure. 1 HNM R and HPLC analysis power of the product, 97% ee (S) -4-chromanol was produced in 99% yield.
  • RuH [(S, S) -Tsdpen] (p-cymene) was synthesized according to the method described in the above-mentioned publicly known document, and a specific procedure is shown below. First, Ru [(S, S)-T sdpen] ( ⁇ -c ym ene) (1 3 0 mg, 0.2 2 mm o 1), 2-propanol 5 ml 1 was charged. Subsequently, after deaeration, the mixture was stirred at room temperature for 14 hours. 2-Propanol was distilled off under reduced pressure (1 mmHg), followed by drying to obtain RuH [(S, S) -Tsdpen] (p-cymene 13 mg).
  • R u (CH 2 NO 2) [(R, R)-T sdpen] ( ⁇ -cymene) was synthesized according to the method described in Organometallics Vol. 21, p253 (2002). The specific procedure is shown below. First, Ru [(R, R)-T sdpen] (p-c ym ene) (1 3 0 mg, 0.22 mm o 1), nitromethane (9 mg, 0.22 mm o 1) and 5 m 1 of methylene chloride were charged. Subsequently, after deaeration, the mixture was stirred at room temperature for 2 hours.
  • C p * I r C l [(R, R)-T sdpen] (C p * represents pentamethylcyclopentene) (1.5 mg, 2 no 1), Y b ( ⁇ ⁇ f) 3 (0. 6 3 mg, 1 m ⁇ 1), 4-Chromanone (0.3 g, 2 mm o 1), KO C (CH 3 ) 3 (0. 2 2 mg, 2 xm ol) was charged and replaced with argon. After adding 2 ml of methanol and pressurizing with hydrogen, it was replaced 10 times. Hydrogen was charged to 30 atm and the reaction was started. After stirring at 50 ° C. for 15 hours, the reaction pressure was returned to normal pressure. From 1 HNMR and HPLC analysis of the product, 96% ee (R) -4-chromanol was produced in 83% yield.
  • Cp * Ir [(S, S) -Tsdpen] was synthesized in accordance with the method described in the above-mentioned publicly known document. The specific procedure is shown below. First, C p * I r C 1 [(S, S)-T sdpen] (2 1 m, 0. 0 3 2 mmo l), 0.1 MN a OH aq (3 2 1, 0. 0 3 2mmol) and methylene chloride 5 ml 1 were charged. Subsequently, the mixture was stirred at room temperature for 3 hours. The solvent was distilled off under reduced pressure (I mmH g), followed by drying to obtain C p * I r [(S, S) -T s d pen] 22 mg. Industrial applicability
  • the present invention is used to produce optically active alcohols as pharmaceuticals, agricultural chemicals, or synthetic intermediates of many general-purpose chemicals.

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Abstract

L'invention concerne un alcool optiquement actif, obtenu en incorporant dans un solvant une cétone, un acide de Lewis et un complexe de ruthénium de formule : et en les mélangeant en présence d'hydrogène de manière à hydrogéner la cétone.
PCT/JP2005/011674 2005-06-20 2005-06-20 Catalyseur d'hydrogenation et procede de fabrication d'un alcool utilisant ce catalyseur WO2006137165A1 (fr)

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GB2451190A (en) * 2007-07-19 2009-01-21 Kanto Kagaku Asymmetric Rhodium and Iridium complexes and their use as catalysts for the asymmetric reduction of ketones to optically active alcohols
CN102119165A (zh) * 2008-07-08 2011-07-06 住友化学株式会社 手性铱水性络合物和使用它的旋光性羟基化合物的制备方法
US9102583B2 (en) 2011-02-25 2015-08-11 China Petroleum & Chemical Corporation Method for producing ethylene glycol from oxalate through the fluidized bed catalytic reaction
CN112745357A (zh) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 一种含有钼和铁的配合物及其制备方法、加氢催化剂及其应用

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2451190A (en) * 2007-07-19 2009-01-21 Kanto Kagaku Asymmetric Rhodium and Iridium complexes and their use as catalysts for the asymmetric reduction of ketones to optically active alcohols
CN102119165A (zh) * 2008-07-08 2011-07-06 住友化学株式会社 手性铱水性络合物和使用它的旋光性羟基化合物的制备方法
US9102583B2 (en) 2011-02-25 2015-08-11 China Petroleum & Chemical Corporation Method for producing ethylene glycol from oxalate through the fluidized bed catalytic reaction
CN112745357A (zh) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 一种含有钼和铁的配合物及其制备方法、加氢催化剂及其应用

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