WO2002004401A1 - Procede de preparation de ?-amino-alcools dans une configuration syn - Google Patents

Procede de preparation de ?-amino-alcools dans une configuration syn Download PDF

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Publication number
WO2002004401A1
WO2002004401A1 PCT/JP2001/005941 JP0105941W WO0204401A1 WO 2002004401 A1 WO2002004401 A1 WO 2002004401A1 JP 0105941 W JP0105941 W JP 0105941W WO 0204401 A1 WO0204401 A1 WO 0204401A1
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group
substituent
transition metal
amino alcohol
syn configuration
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PCT/JP2001/005941
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English (en)
Japanese (ja)
Inventor
Tsutomu Inoue
Eiji Katayama
Hirohito Ooka
Daisuke Sato
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Nippon Soda Co., Ltd.
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Priority to JP2002509069A priority Critical patent/JP5042438B2/ja
Publication of WO2002004401A1 publication Critical patent/WO2002004401A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton

Definitions

  • the present invention uses a racemic diaminocarbonyl compound as a starting material to produce S-amino alcohols having a syn configuration useful as a synthetic intermediate for pharmaceuticals and agrochemicals, with high yield and high diastereoselectivity. Further, it relates to a technology for selectively manufacturing high-tech Nancho. Background technology:
  • An object of the present invention is to provide a practical method for producing optically active 3-amino alcohols having a syn configuration by using a readily available racemic aminopulponyl compound as a starting material.
  • methods (1) and (2) have a high anti-isomer production rate and are not suitable for the production of general syn-isomer.
  • the methods (2) and (3) are complicated because the raw material of the optically active substance must be manufactured in advance, and the method (2) requires a substrate containing a functional group such as a lipoxyl group in the molecule.
  • High stereo stereo selection Although it is possible to produce an optically active amino alcohol by its nature, it is difficult to produce an optically active form of a simple amino alcohol having no such functional group in the molecule.
  • a syn isomer (a compound having a syn configuration), which means one of the diastereoisomers, means that when a carbon chain is placed in a zigzag left and right direction with a carbon chain as a main chain, the carbon is substituted in the up and down direction, respectively. Having a steric configuration such that the amino group and the hydroxyl group face the same plane.
  • the present inventors have conducted intensive studies on conditions for synthesizing syn isomers with superiority, and as a result, have found that a substituent of an amino group has a great effect on diastereoselectivity, and thus completed the present invention.
  • Ra and Rc are the same or different and each may be an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an alkenyl which may have a substituent. And a aralkyl group which may have a substituent, an aryl group which may have a substituent, and an aryloxy group which may have a substituent, respectively.
  • Rb represents any one of the following general formulas (3), (4), (5), and (6).
  • Rl, Rl 'and R2 are the same or different and each represents a 7] elementary atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, May have Cycloalkyl group, cycloalkyl group optionally having substituent (s), alkenyl group optionally having substituent (s), aralkyl group optionally having substituent (s), optionally having substituent (s)
  • a nitrogen-containing hetero ring of the member may be formed.
  • R 1 is not an alkoxy group, a cycloalkoxy group, an aryloxy group, or an aralkyloxy group.
  • R a, R b and R c have the same meanings as described above, and C * represents an asymmetric carbon atom.
  • the transition metal compound is preferably a homogeneous hydrogenation catalyst.
  • the homogeneous hydrogenation catalyst is more preferably represented by the following general formula (7)
  • Ma represents a Group VIII metal atom
  • X and Y are the same or different and represent a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group or an alkoxyl group
  • Px represents a phosphine ligand
  • Nx represents an amine ligand
  • m and n represent 0 or an integer of 1 to 4).
  • the base may be represented by the following general formula (8):
  • Mb represents an alkali metal or alkaline earth metal
  • Z is represents hydroxy group, an alkoxy group having 1 to 6 carbon atoms, a mercapto group, an aromatic group, or C0 3 group a
  • an optically active transition metal compound in the present invention an optically active / 3-amino alcohol having a syn configuration can be obtained.
  • an optically active transition metal compound in which both P ⁇ and Nx in the general formula (7) are optically active, or one of them is optically active can be used.
  • a racemic S-amino alcohol having a syn configuration can be obtained by using an optically inactive transition metal compound.
  • an optically inactive transition metal complex an optically inactive transition metal complex in which both Px and Nx in the general formula (7) are optically inactive can be used.
  • both PX and Nx are optically inactive, it means that these ligands are racemic, or that they are ligands having no asymmetric center.
  • an optically active amino alcohol having a syn configuration represented by the general formula (2) having a syn configuration useful as a synthetic intermediate for pharmaceutical and agricultural chemicals can be obtained with high selectivity and high yield. Can be manufactured to rate.
  • the present invention is characterized in that, as described above, hydrogen or a compound that provides hydrogen is allowed to act on the aminocarbonyl compound represented by the general formula (1) in the presence of a transition metal compound and a base.
  • This is a method for producing 3-amino alcohols having a syn configuration represented by the general formula (2).
  • the starting compound of the present invention is a compound represented by the following general formula (1).
  • Ra and Rc are the same or different and each may be a linear or branched alkyl group which may have a substituent, a linear or branched alkenyl group which may have a substituent, or a substituent.
  • Ra or Rc may have a substituent (linear or branched alkyl group, linear or branched alkenyl group, cycloalkyl group, aralkyl group or aryl group). There are no particular restrictions on the substitution position, the type of substituent, the number of substituents, and the like, as long as the substituent does not inhibit the reaction.
  • Such substituents include, for example, hydroxy, carboxyl, amino,
  • Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, 1; -butyl, pentyl, and hexyl;
  • Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, etc.
  • Alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl group, and a phenyl group which may have a substituent at any position of the benzene ring ,
  • a naphthyl group such as 1-naphthyl or 2-naphthyl group which may have a substituent at any position of the naphthalene ring;
  • a heterocyclic group (these groups may have a substituent at any position);
  • halogen atoms such as fluorine, chlorine, and bromine.
  • An alkyl group of a linear or branched alkyl group which may have the substituent may be methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-Examples include alkyl groups having 1 to 20 carbon atoms, such as pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, and icosyl groups.
  • alkenyl group of the linear or branched alkenyl group which may have a substituent examples include vinyl, 1-propenyl, 2-propenyl, 1-isopropenyl, 1-butenyl, and 1-isopropyl.
  • alkenyl groups having 2 to 20 carbon atoms such as propenyl, 2-butenyl, 3-butenyl, 1,3-butenyl, 11-pentenyl, 2_pentenyl, 3-pentenyl, and 2-hexene. it can.
  • cycloalkyl group of the optionally substituted cycloalkyl group examples include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. .
  • aralkyl group of the aralkyl group which may have a substituent examples include, for example, aralkyl groups having 7 to 20 carbon atoms such as benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ 3 ⁇ 4-dimethylbenzyl and ⁇ -ethylbenzyl groups. Can be mentioned.
  • aryl group of the aryl group which may have a substituent examples include aromatic hydrocarbon groups such as phenyl, 1-naphthyl and 2-naphthyl groups; Oxygen-containing heterocyclic groups such as furanyl, bilanyl, and dioxolanyl;
  • I-containing heterocyclic groups such as chenyl
  • Rb represents any one of the following general formulas (3), (4), (5), and (6).
  • R1 2N- wherein R 1, R ⁇ and R 2 are the same or different and each have a hydrogen atom, a formyl group, an alkyl group which may have a substituent, or a substituent.
  • R2 or R1 and R1 ′ may combine to form a 5- to 8-membered nitrogen-containing heterocycle.
  • R 1 is not an alkoxy group, a cycloalkoxy group, an aryloxy group, or an aralkyloxy group.
  • R 2 is a hydrogen atom
  • R 1 is an alkoxy group, a cycloalkoxy group, an aryloxy group, or an aralkyloxy group
  • 3-amino alcohol having an anti-steric configuration which is not the object compound of the present invention is dominant. Because it is generated.
  • Rb is the general formula (3) RI CO (R2) N—
  • Rl and R2 are an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent
  • a cycloalkyl group optionally having a substituent, a cycloalkoxy group optionally having a substituent, an alkenyl group optionally having a substituent, an aralkyl group optionally having a substituent, a substituent R 1 and R 2 are bonded to each other when R 1 and R 2 are a aralkyloxy group which may have a substituent, an aryl group which may have a substituent or an aryl group which may have a substituent, or 5 To 8-member nitrogen containing When a terrorist ring is formed, the selectivity of the syn stereoisomer is high, which is preferable.
  • R 1, R 1 ′ and R 2 in R b are specifically a hydrogen atom
  • a cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
  • Phenyl group 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 2-t-butylphenyl, 2-methoxyphenyl, 2-chlorophenyl, 2-vinylphenyl, 3-methylphenyl, 3-ethylphenyl, 3- ⁇ Tso Propylphenyl, 3-methoxyphenyl, 3-chlorophenyl, 3-vinylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylisopropyl, 4-t-butylphenyl, 4-vinylphenyl, cumenyl, mesityl , An xylyl group, an aryl group which may have a substituent such as 1-naphthyl, 2-naphthyl, anthryl, phananthryl, indenyl group,
  • Aralkyl groups having 7 to 20 carbon atoms which may have a substituent such as benzyl, 4-cyclobenzyl, and ⁇ -methylbenzyl;
  • Alkenyl groups having 2 to 10 carbon atoms such as vinyl, aryl, and crotyl groups
  • Examples thereof include an alkoxy group having 1 to 10 or a cycloalkoxy group having 3 to 8 carbon atoms.
  • Phenoxy group 2-methyl phenoxy, 2-ethyl phenoxy, 2-isopropyl phenoxy, 2_t-butyl phenoxy, 2-methoxy phenoxy, 2-chloro phenoxy, 2-vinyl phenoxy, 3-methyl phenyl, 3-ethyl phenoxy, 3-isopropyl Phenoxy, 3-methoxyphenoxy, 3-chlorophenoxy, 3-vinylphenoxy, 4-methylphenoxy, 4-ethylphenoxy, 4 ⁇ T-sopropylphenoxy, 41-t-butylphenyloxy, 4-vinylphenoxy, Aralkyl groups such as 1-naphthoxy, 2-naphthoxy and other aryloxy groups, benzyloxy, 4-chlorobenzyloxy and 4-methylbenzyloxy groups And an aralkyloxy group having 7 to 20 carbon atoms which may have a substituent such as an oxy group.
  • heterocycle examples include succinimid, maleimid, phthalimid, and 1,2-cyclohexanecarboxy. And imids such as amide, 2,4,6-trioxopiperidine, ⁇ -pyridone and the like.
  • R b More specific examples of R b include acetylamino, propionylamino, propylcarbonylamino, benzoylamino, 4-methylbenzoylamino, 2-methylbenzoylamino, 3-methoxybenzoylamino, and 2-methoxybenzoylamino.
  • 4-Aminamino groups such as methoxybenzoylamino groups
  • Diacetylamino groups such as diacetylamino, dibenzoylamino group,
  • N-acetyl-N-phenylamino N-acetyl-N-4-methylphenylamino, N-acetyl-N-2-chlorophenylamino, N-acetyl-N-2,4-dichlorophenylamino, N-benzyl N- such as N-phenylamino, N-benzyl-1-N-4-methylphenylamino, N-benzylyl N-2-chlorophenylamino, N-benzyl-N-2,4-dichlorophenylamino Aryl-N-acylamino group,
  • Succinimidyl maleimidyl, phthalimidyl, 3-methylphthalimidyl, 4-methylphthalimidyl, 4-n-butylphthalimidyl, 4 Imid groups such as phthalimidyl group, tetramethylphthalimidyl group, 1,2-cyclohexanecarboxamidoyl group, 2,4,6-trioxopiperidine-11-yl group, ⁇ -pyridone-11-yl group, etc. Can be mentioned.
  • the transition metal compound used in the present invention is preferably a homogeneous hydrogenation catalyst.
  • a homogeneous hydrogenation catalyst for example, a transition metal complex of a Group VIII element of the periodic table such as Ru, Rh, Ir, or Pt is preferable.
  • These transition metal compounds can be synthesized and obtained by the method described in, for example, Angew. Cem. Int. Ed., 3_, 1703 (1998).
  • the transition metal compound is more preferably a transition metal complex represented by the general formula (7).
  • Ma represents a Group VIII metal atom
  • X and Y are the same or different and represent a hydrogen atom, a halogen atom, a hydroxyl group or an alkoxy group
  • Px represents a phosphine ligand
  • Nx represents And m and n each represent 0 or an integer of 1 to 4.
  • Ma represents a Group VIII metal such as Ru, Rh, Ir, and Pt.
  • a Ru complex is particularly preferable in view of the stability of the complex and availability.
  • X and Y are the same or different and each represent a hydrogen atom, a halogen atom such as fluorine, chlorine, or bromine, a carboxyl group, a hydroxyl group, a methoxy, ethoxy, a propoxy, an isopropoxy, or a butoxy group.
  • a halogen atom such as fluorine, chlorine, or bromine
  • the phosphine The Px is a ligand, for example, the general formula PR A R B R C with phosphorus monodentate ligand represented and R D R E P- W_P R F 2 of phosphorus represented by R G And the like.
  • R A R B R C , R A , R B , and R c are the same or different and each represent an alkyl group, a phenyl group or a cycloalkyl group which may have a substituent, And two of R A , R A , R B and R c may be taken together to form an alicyclic group which may have a substituent.
  • the general formula PR A R B R C is optically active.
  • all of R A , R B , and R c are optically inactive groups, and when at least two are the same, the general formula PR A R B R C is optically inactive.
  • R D R E P- W- PR F R G, R D ⁇ E R F, R G are the same or different from Represents an alkyl group, a phenyl group or a cycloalkyl group which may have a substituent, and may have a substituent when R D and R E or R F and R G are taken together.
  • Good alicyclic groups may be formed.
  • W represents a hydrocarbon group having 1 to 5 carbon atoms, a cyclohydrocarbon group, an aryl group, an unsaturated hydrocarbon group, or the like.
  • Examples of monodentate phosphine ligands represented by the general formula PR A R B R C is, for example, trimethyl chill phosphine, tri E chill phosphine, tributyl phosphine, triphenyl phosphine, cyclohexyl phosphine to tricyclo, tri (p- tolyl ) Phosphine, diphenylmethylphosphine, dimethylphenylphosphine, isopropylmethylphosphine, cyclohexyl (0-anisyl) monomethylphosphine, 1- [2- (diphenylphosphino) fluorocenyl] ethyl methyl ether, 2 Tertiary phosphines such as — (diphenylphosphino) 1-2′-methoxy-1, 2-binaphthyl and the like are preferred. Further, a phosphine ligand in which R A , R B , and R
  • the above-mentioned general formula 1 13 1 £ ⁇ —1 ⁇ _? 1 ⁇ > 1.
  • an optically active bidentate phosphine ligand such as bisdiphenylphosphinomethane, bisdiphenylphosphinoethane, bisdiphenylphosphinopropane, bisdiphenyl.
  • Suitable examples include bidentate tertiary phosphine compounds such as phosphinobutane, bisdimethylphosphinoethane, and bisdimethylphosphinopropane.
  • bidentate phosphine ligands include, for example, BI NAP: 2,2'-bis- (diphenylphosphino) -11, ⁇ -binaphthyl, an alkyl group and a aryl group on the naphthyl ring of BI NAP.
  • BI NAP derivative having a substituent for example, H 8 BI NAP
  • BI NAP-induced body 1-5 pieces have a substituent of an alkyl group such as a benzene ring bonded to the phosphorus atom such as BI NAP, for example, Xy 1 y 1 —BI NAP: 2, 2 ′ —bis- (di-1,5-xylylphosphino) -1,1, ⁇ —binaphthyl, and BI CHEP : 2, 2 ′ —bis- (dicyclohexylphosphino) 1,6,6 ′ —Dimethyl-1,1,1-biphenyl, BPPFA: 1— [ ⁇ , 2-bis (diphenylphosphine) fuerocenyl] ethyldiamine, CH I RAPHOS: 2,3-bis (diphenylphosphine) butane, CYCPHOS: 1-cyclohexyl-1,2-bis-1 (
  • R H , R or Rj are the same or different and represent 7j element, an alkyl group, an aryl group, or an unsaturated hydrocarbon group, and two of R H and Rj are the same.
  • An alicyclic group which may have a substituent may be formed.
  • at least one of R H and R : Rj may be an optically active group.
  • R K R L N- X- NR M R N, R K, R have R M, R N, taken identical or different from, 7Jc group, an alkyl group, Ariru group or unsaturated hydrocarbon group the stands may be formed R K and R L or R M and R N are together a connexion which may have a substituent alicyclic group.
  • X represents an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group, an aryl group, an unsaturated hydrocarbon group, or the like.
  • Examples of the monoamine ligand represented by the general formula NR H RiR j include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclopentylamine, cyclohexylamine, benzylamine, dimethylamine, getylamine, zipamine.
  • Monoamine compounds such as dihexylamine, dicyclopentylamine, dicyclohexylamine, dibenzylamine, diphenylamine, phenylethylamine, proline and piperidine can be exemplified.
  • optically active monoamine ligand examples include optically active monoamine compounds such as optically active phenylethylamine, naphthylethylamine, cyclohexylamine, and cycloheptylethylenediamine.
  • Optically active diamine ligands include optically active 1,2-diphenylethylenediamine, 1,2-cyclohexanediamine, 1,2-cycloheptanediamine, 2,3-dimethylbutandiamine, 1-Methyl_2,2-diphenylethylenediamine, 1-butyl-2,2-diphenylethylenediamine, 1-isopropyl-1,2,2-diphenylethylenediamine, 1-methyl-1,2,2-diphenylethylenediamine 2-di (P-methoxyphenyl) ethylenediamine, 1-isobutyl-1,2,2-di (p-methoxyphenyl) ethylenediamine, 1-isopropyl-1,2,2-di (P-methoxyphenyl) ethylenediamine, 1-Benzyl-1,2,2-di (p-methoxyphenyl) ethylenediamine, 1-methyl-1,2,2-dinaphthylethylenediamine, 1_isobutyl-2,2-dinap
  • optically active diamine compound is not limited to the exemplified optically active diamine derivatives, and optically active propanediamine, butanediamine, phenylenediamine, cyclohexanediamine derivatives and the like can also be used.
  • the amine ligand that can be used in the present invention is not limited to these as long as it can form a metal complex stably.
  • the amount of the homogeneous hydrogenation catalyst used depends on the type of the reaction substrate, the reaction vessel and the economical efficiency, etc., but is usually 1100-1 / molar ratio with respect to the carbonyl compound as the reaction substrate. 10,000,000, preferably 1/200 to: L / 100,000.
  • the base used in the present invention is a compound represented by the general formula (8),
  • M b represents an alkali metal or an alkaline earth metal
  • Z is an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, and propoxy;
  • Aryl groups such as phenyl and naphthyl
  • Examples of the base KOH, KOCH 3, KOCH ( CH 3) 2, KOC (CH 3) 3, KC 10 H 8, NaOH, NaOCH 3, L i OH, L i OCH 3, L i OCH (CH 3) 2 Mg (OC 2 H 5) 2, Na SH, the K 2 C0 3, C s 2 C 0 3 or the like can be exemplified.
  • a quaternary ammonium salt can be similarly used as the base.
  • the amount of the base to be used is generally 0.5 to 100 equivalents, preferably 2 to 40 equivalents, relative to the Group VIII transition metal complex.
  • the reaction is carried out by dissolving the ⁇ -aminocarbonyl compound represented by the general formula (1) as a substrate in an inert solvent, and reacting with hydrogen or hydrogen in the presence of a predetermined amount of a transition metal complex and a base. This is done by applying an object.
  • the solvent that can be used for the reaction is not particularly limited as long as it is inert and solubilizes the reaction raw material (substrate) and the catalyst system.
  • solvents include, for example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane and octane; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; Ethers, ethers such as tetrahydrofuran, alcohols such as methanol, ethanol, 2-propanol, butanol, benzyl alcohol, acetonitrile, DMF ( ⁇ , ⁇ -dimethylformamide), ⁇ ⁇ ⁇ -methylpyrrolidone, pyridine, Organic solvents containing a heteroatom such as DMSO (dimethyl sulfoxide) can be mentioned.
  • aromatic hydrocarbons such as benzene
  • alcohol-based solvents are particularly preferred because the product is an alcohol.
  • These solvents can be used alone or as a mixed solvent thereof.
  • the amount of the solvent used is determined based on the solubility of the reaction substrate, the economic efficiency, and the like.
  • the concentration of the substrate can be as low as 1% or less and in a state close to no solvent containing only the substrate.
  • the concentration is 20 to 50% by weight. it can.
  • the reaction is carried out in the presence of hydrogen gas or a compound donating hydrogen.
  • hydrogen gas it is desirable that the hydrogen pressure in the system is 1 to 200 atm, preferably 3 to 100 atm.
  • Compounds that donate hydrogen include hydride complexes and hydrogen storage alloys.
  • the reaction temperature is ⁇ 30 to 100 ° C., preferably 15 to 100 ° C. in consideration of the reaction rate and the like. It can be carried out even at around room temperature of 25 to 40 ° C.
  • the reaction depends on the reaction substrate concentration, temperature, It usually takes several minutes to 10 hours, depending on the reaction conditions such as pressure.
  • the reaction may be of a batch type or a continuous type.
  • rl represents an alkoxy group, a cycloalkoxy group, an alkenyloxy group, an aralkyloxy group, or an aryloxy group, and R2 and Rl 'are the same as described above.
  • the oxazolidinone derivative When the oxazolidinone derivative is produced, it can be treated with an acid or a base to obtain a syn configuration / 3-amino alcohol.
  • the following table shows examples of the compound represented by the general formula (2) and the compound represented by the general formula (1), which is a starting material, which can be produced by the present invention.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • S-amino alcohols having a syn-configuration useful as a synthetic intermediate for pharmaceuticals and agrochemicals can be produced in a highly selective, high yield, and industrially advantageous manner in both racemic and optically active forms.

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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
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Abstract

L'invention concerne un procédé de préparation de β-amino-alcools dans une configuration syn représentée par la formule générale (2) : RaC*H(OH)-C*H(Rb)-Rc (2), dans laquelle Ra et Rc sont substitués facultativement et respectivement à un alkyle ou similaire, Rb représente un groupe sélectionné parmi ceux représentés par les formules comprises entre (3) et (6) : (3)R1CO(R2)N-, (4)R1CO(R1'CO)N-, (5)R1SO2(R2)N-, et (6)R1R2N-, dans lesquelles R?1, R1' et R2¿ sont substitués facultativement et respectivement par un alkyle ou similaire), et C* représente un atome de carbone asymétrique. Ledit procédé consiste à faire réagir un composé α-aminocarbonyle de la formule générale (I) R¿a?-CO-CH(Rb)-Rc (I) avec de l'hydrogène ou un donneur d'hydrogène en présence d'un composé métallique de transition et d'une base.
PCT/JP2001/005941 2000-07-10 2001-07-09 Procede de preparation de ?-amino-alcools dans une configuration syn WO2002004401A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7488833B2 (en) 2002-08-27 2009-02-10 Merck Patent Gmbh Process for the enantioselective hydrogenation of amino alcohols
WO2009125565A1 (fr) * 2008-04-07 2009-10-15 日本曹達株式会社 Composé du ruthénium et procédé de fabrication d'un composé d'aminoalcool optiquement actif
WO2012081582A1 (fr) * 2010-12-15 2012-06-21 国立大学法人北海道大学 Procédé de fabrication de composé alcool de manière diastéréosélective, et composé ruthénium
US8759524B2 (en) 2007-09-06 2014-06-24 Nippon Soda Co., Ltd. Production process of optically active 3-quinuclidinol derivative
JP2016199513A (ja) * 2015-04-13 2016-12-01 国立大学法人名古屋大学 カルボン酸化合物の水素化によるアルコールの製造方法、及び該製造方法に用いるルテニウム錯体
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US8759524B2 (en) 2007-09-06 2014-06-24 Nippon Soda Co., Ltd. Production process of optically active 3-quinuclidinol derivative
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US8207379B2 (en) 2008-04-07 2012-06-26 Nippon Soda Co., Ltd. Ruthenium compound and method for producing optically active aminoalcohol compound
KR101243408B1 (ko) * 2008-04-07 2013-03-13 닛뽕소다 가부시키가이샤 루테늄 화합물 및 광학 활성 아미노알코올 화합물의 제조 방법
JP5276093B2 (ja) * 2008-04-07 2013-08-28 日本曹達株式会社 光学活性アミノアルコール化合物の製造方法
KR101808261B1 (ko) 2010-04-28 2017-12-12 다카사고 고료 고교 가부시키가이샤 루테늄 착체 및 광학적으로 활성인 알코올 화합물의 제조방법
WO2012081582A1 (fr) * 2010-12-15 2012-06-21 国立大学法人北海道大学 Procédé de fabrication de composé alcool de manière diastéréosélective, et composé ruthénium
JP5616976B2 (ja) * 2010-12-15 2014-10-29 国立大学法人北海道大学 ジアステレオ選択的にアルコール化合物を製造する方法及びルテニウム化合物
JP2016199513A (ja) * 2015-04-13 2016-12-01 国立大学法人名古屋大学 カルボン酸化合物の水素化によるアルコールの製造方法、及び該製造方法に用いるルテニウム錯体

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