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WO2002008170A1 - Procede de production de derives de $g(a)-amino-$g(a), $g(a)', $g(a)'-trihalocetone, de derives de $g(a)-amino-$g(a)', $g(a)', $g(a)'-trihaloalcool et de derives d'acide $g(a)-hydroxy-?-aminocarboxylique - Google Patents

Procede de production de derives de $g(a)-amino-$g(a), $g(a)', $g(a)'-trihalocetone, de derives de $g(a)-amino-$g(a)', $g(a)', $g(a)'-trihaloalcool et de derives d'acide $g(a)-hydroxy-?-aminocarboxylique Download PDF

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Publication number
WO2002008170A1
WO2002008170A1 PCT/JP2001/006317 JP0106317W WO0208170A1 WO 2002008170 A1 WO2002008170 A1 WO 2002008170A1 JP 0106317 W JP0106317 W JP 0106317W WO 0208170 A1 WO0208170 A1 WO 0208170A1
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group
production method
atom
amino
hydrogen atom
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English (en)
Japanese (ja)
Inventor
Katsuharu Maehara
Toshihiro Takeda
Yasuyoshi Ueda
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Kaneka Corp
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Kaneka Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
    • 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
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to a method for producing an optically active ⁇ -hydroxyl; 8_aminocarboxylic acid derivative useful as an intermediate of a pharmaceutical 'pesticide'.
  • a method for producing an optically active ⁇ -hydroxy-1-aminocarboxylic acid derivative includes, for example, a method in which a ⁇ -protected aldehyde derivative is silylated by reaction with silyl cyanide and then hydrolyzed (Japanese Unexamined Patent Publication No. 2-28). No. 144), a method in which a ⁇ -protected aldehyde derivative is cyanated and hydrolyzed in the presence of a phase transfer catalyst and acetic anhydride (Japanese Patent Application Laid-Open No. 2-017171), and a ⁇ -protected aldehyde derivative as well.
  • an object of the present invention is to provide an optically active ⁇ -hydroxy with high efficiency and simple operation.
  • An object of the present invention is to provide a method for producing a C / 3 / 3-rubonic acid derivative.
  • the present inventors have conducted intensive studies in view of the above-mentioned current situation, and as a result, have completed a production method represented by the following reaction formula.
  • R 1 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms.
  • X represents an unsubstituted aryl group
  • X 1 , 2 and 3 each independently represent a halogen atom, and one represents a hydrogen atom and the other represents a protecting group for an amino group, Together or each represents a protecting group for an amino group, or each represents a hydrogen atom.
  • the ⁇ -amino-o a-trihalo alcohol derivative (1) is represented by the following general formula (3)
  • the ⁇ -amino-a ′, a ′ a trihaloketone derivative (3) is represented by the following general formula (4)
  • X 4 represents the X 1 or a hydrogen atom.
  • X 5 represents the X 2 or a hydrogen atom. However, X 4 and X 5 simultaneously represent a hydrogen atom Excluding the case. )) Can be obtained by halogenating the ⁇ -aminoketone derivative represented by
  • the ⁇ -aminoketone derivative (4) is represented by the following general formula (5)
  • the present invention also relates to a method for producing an ⁇ -amino-'′, ⁇ ′, ⁇ ′-trihaloketone derivative (3) comprising halogenating an ⁇ -aminoketone derivative (4).
  • the present invention also provides a method for producing an amino-, a ', a'-trihaloalcohol derivative (1), comprising reducing the obtained ⁇ -amino_', a ', a'-trihaloketone derivative (3).
  • the present invention provides the above amino-ketone derivative (4) obtained by reacting the amino acid ester derivative (5) with a monohaloacetic acid derivative or a salt thereof, or dihalomethane.
  • the method for producing the ⁇ ′, ⁇ ′-trihaloketone derivative (3) and the method for producing the ⁇ ; —amino-, a ′, a′-trihaloalcohol derivative (1) described above are also used.
  • X 6 , 7 and 8 independently represent a bromine atom or a chlorine atom.
  • P 1 and P 2 each represent a hydrogen atom and the other represents a protecting group for an amino group, Or together Or represents an amino protecting group.
  • ⁇ -amino ',', a 'monotrihaloketone derivatives represented by the following general formula (7)
  • X 6 , X 7 and X 8 independently represent a bromine atom or a chlorine atom.
  • P 1 and P 2 each represent a hydrogen atom and the other represents a protecting group for an amino group. , Or together or each represents a protecting group for an amino group.
  • X 1 , 2 and 3 independently represent a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and a iodine atom
  • X 2 and X 3 are preferably independently a chlorine atom or a bromine atom.
  • X 1 is a chlorine atom
  • X 2 and X 3 are independently a chlorine atom or a bromine atom
  • X 1 and X 2 are each a bromine atom
  • X 3 is a chlorine atom or a bromine It is preferably an atom.
  • X 1 , X 2 and X 3 are preferably all the same atom, and X 1 , X 2 and X 3 are all chlorine atoms, or X 1 , X 2 and X 3 Are more preferably all bromine atoms.
  • X 1 is a chlorine atom and 2 and 3 are independently a chlorine atom or a bromine atom. It is particularly preferred that all of X 1 , X 2 and X 3 are chlorine atoms.
  • X 4 represents the aforementioned X 1 or a hydrogen atom
  • X 5 represents the aforementioned X 2 or a hydrogen atom.
  • X 4 and X 5 simultaneously represent a hydrogen atom. Due to the ease of synthesis of the above compound (4), X 4 is a chlorine atom Or X 5 is a hydrogen atom (especially when X 4 is a chlorine atom and X 5 is a hydrogen atom), or X 4 and X 5 are each a bromine atom Is preferred.
  • X 6 , 7 and 8 independently represent a bromine atom or a chlorine atom.
  • One of X 6 , X 7 and X 8 is a chlorine atom and the remaining two are each a chlorine atom or a bromine atom, or two of them are each a bromine atom and the other one is a chlorine atom or a bromine atom
  • X 6 , X 7 and X 8 are particularly preferably chlorine atoms or all bromine atoms.
  • P 1 and P 2 represent a protecting group for an amino group or a hydrogen atom.
  • Amino groups or other one represents a hydrogen atom
  • P 1 ⁇ Pi P 2 represents a protecting group of the Amino group, or represents a protecting group together such connexion amino group, or, respectively
  • Amino groups Represents a protecting group.
  • “ 1 and P 2 together represent a protecting group for an amino group” means that the amino group is protected by a bifunctional protecting group such as a phthalyl group.
  • the above-mentioned protecting group for the amino group is generally a group having an effect of protecting the amino group, and examples of usable groups include, for example, PROTECT I VE GROUPS IN ORGAN IC SYNTHES IS) [2nd edition, John Wiley & Sons (1991)].
  • the amino-protecting group is not particularly limited, and examples thereof include a urethane-type protecting group, an acyl-type protecting group, and an alkyl-type protecting group.
  • the urethane-type protecting group is not particularly limited, and includes, for example, a benzyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbo group, and the like.
  • acetyl-type protecting group is not particularly limited, and examples thereof include an acetyl group, a trifluoroacetyl group, a phthaloyl group, a benzoyl group, and a tosyl group.
  • the alkyl-type protecting group is not particularly limited, and examples thereof include a methyl group, a benzyl group, and a dibenzyl group.
  • P 1 and P 2 represents a hydrogen atom and the other represents a protecting group for an amino group
  • benzyl / reoxy / reponyl methoxycanoleponyl, ethoxycarbonyl, tert-butoxycarbyl, acetyl, trifluoroacetyl, benzoyl, tosyl, methyl, benzyl, etc.
  • group which together form a protecting group for an amino group include a phthaloyl group.
  • examples of P 1 and P 2 each representing an amino-protecting group include, for example, one of the above-mentioned alkyl-type protecting groups such as a methyl group and a benzyl group, and the other being a benzyloxycarbonyl group or a methoxycarbonyl group.
  • the above urethane-type protecting group such as a group; one is the above-mentioned alkyl-type protecting group such as a methyl group or a benzyl group, and the other is the above-mentioned acyl-type protecting group such as an acetyl group or a trifluoroacetyl group.
  • P 1 and P 2 are independently an alkyl group such as a methyl group or a benzyl group; or when both are the same alkyl group (for example, a dimethyl group, a dibenzyl group, etc.) ) And the like.
  • a one is hydrogen atom or the alkyl type protecting groups P 1 and P 2, is preferably other is the urethane type protecting group, especially, 1 ⁇ Pi? It is preferable that one of the two is a hydrogen atom and the other is a urethane-type protecting group.
  • P 1 or P 2 one of P 3 and P 4 are alkyl le type protecting group is a hydrogen atom, or, is preferably a hydrogen atom, respectively it, among other things, P 3 And each of P 4 is preferably a hydrogen atom.
  • the above compound (1) is hydrolyzed to obtain the above compound (2). It is preferred to remove the urethane-type protecting group.
  • R 1 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 30 carbon atoms or Represents an unsubstituted aralkyl group or a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms.
  • the above-mentioned substituted or unsubstituted alkyl group having 1 to 30 carbon atoms is not particularly limited, and examples thereof include a meth / yl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexylmethyl group, a tert-butyl group, and a hydroxymethyl group.
  • a meth / yl group an ethyl group, an isopropyl group, an isobutyl group, a cyclohexylmethyl group, a tert-butyl group, and a hydroxymethyl group.
  • the substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms is not particularly limited. Examples thereof include a benzyl group, a p-hydroxybenzyl group, a p-methoxybenzyl group, an a-phenethyl group, and a 3-phenyl group. Examples include an enylpropyl group and a 2-phenylpropyl group.
  • the substituted or unsubstituted aryl group having 6 to 30 carbon atoms is not particularly limited. Examples thereof include a pheninole group, a p-hydroxypheninole group, a p-methoxypheninole group, and a p-chlorophene group. Examples thereof include a binore group, a p-funoleolopheninole group, an 11-naphthinole group, and a 2-naphthinole group.
  • the above carbon number of 7 to 30 such as a benzyl group, a p-hydroxybenzyl group, a p-methoxybenzyl group, an ⁇ -phenyl / ethylene group, a 3-phenylpropyl group, and a 2-phenylpropyl group.
  • a substituted or unsubstituted aralkyl group is particularly preferable, an unsubstituted aralkyl group having 7 to 30 carbon atoms is particularly preferable, and a benzyl group is particularly preferable.
  • R 2 represents an ester residue.
  • the above ester residue represents a monovalent organic group which may be the Furudo included in the structure represented in one COOR 2, it acts as an ester-type protective group for carboxyl group.
  • the monovalent organic group is not particularly limited as long as it has an effect of protecting the carboxyl group.
  • PROTECT I VE GROUP SIN ORGAN ICS YN THE SIS [Second Edition, John Wiley & Sons (1991)]
  • a lower alkyl group having 1 to 4 carbon atoms a substituted or unsubstituted benzyl group is preferable, a lower alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are more preferable. A methyl group is particularly preferred.
  • the compound (1) is hydrolyzed to the compound (2) in the presence of water with steric inversion of the hydroxyl group at the 2-position.
  • the hydrolysis reaction is carried out using a general hydrolysis method, and it is particularly preferable to carry out the hydrolysis under basic conditions (in the presence of a base).
  • the base is not particularly limited, but it is particularly preferable to use an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, and rhodium hydroxide.
  • the equivalent of the base is usually required to be at least about 3 molar equivalents, and preferably about 5 to 10 molar equivalents. However, the type and amount of the base to be used are not limited to these, and can be appropriately determined as necessary by a simple experiment.
  • reaction solvent is not particularly limited, for example, a mixed system of water and an organic solvent or an aqueous system is preferable, and an aqueous system is particularly preferable.
  • an organic solvent when used in combination, it may be water-soluble or water-insoluble, for example, ketones such as acetone, hydrocarbons such as toluene, ethers such as tetrahydrofuran, and polar aprotic solvents such as acetonitrile.
  • hydrocarbon can be used, it is preferable to use hydrocarbons, especially toluene, from the viewpoint of economy and availability.
  • the reaction temperature is not particularly limited, but generally, a high temperature of 40 ° C. or higher is preferable for terminating the reaction quickly. If a urethane-type protecting group is present on the amino group of compound (1), the urethane-type protecting group is removed by performing a hydrolysis reaction at a high temperature or by increasing the temperature after the hydrolysis reaction. (Desorption) is also possible.
  • the reduction method is not particularly limited.
  • hydrides such as sodium bis (2-methoxy-ethoxy) aluminum hydride, lithium aluminum hydride, sodium borohydride, potassium borohydride, tetramethylammonium borohydride; Minimum triisopropoxide and The aluminum tri alkoxide ( ⁇ Rukokishiru group such as an aluminum tree s e c- butoxide, preferably 1-1 carbon atoms 0, more preferably 1 to carbon atoms
  • lithium aluminum trialkyl hydride such as tert-butoxy hydride (alkoxyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms); methanesulfonolate Substituted aluminum alkoxides such as oxynoreminidium diisopropoxide ethanesulfonyloxy anoremyium disopropoxide (the substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) Which is an alkylsulfonyloxy group).
  • tert-butoxy hydride alkoxyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms
  • methanesulfonolate Substituted aluminum alkoxides such as oxynoreminidium diisopropoxide ethanesulfonyloxy anoremyium disopropoxide (the substituent preferably has 1 to 10 carbon atoms,
  • dialkylaluminum hydride preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably diisobutylaluminum hydride
  • an alcohol preferably an alkyl group having 1 to 10 carbon atoms
  • 2-propanol see, for example, JP-A-6-206877, JP-A-8-208. —1099-131, JP-A-8-225555, JP-A-198995, Japanese Patent Application No. 9-162505, etc.
  • hydrides such as sodium borohydride and aluminum trialkoxides such as aluminum triisopropoxide are preferably used.
  • the reducing agent is generally effective for diastereoselectively producing the compound (1).
  • the equivalent of the reducing agent is determined by the type of the reducing agent and the reducing ability per mole of the reducing agent. For example, when sodium polohydride or aluminum triisopropoxide is used, it is generally used in a molar amount of 1 to 2 times.
  • the reaction solvent is not particularly restricted but includes, for example, alcohols such as methanol and 2-propanol, hydrocarbons such as toluene, and ethers such as tetrahydrofuran.
  • the reaction temperature cannot be uniformly defined depending on the type of the reducing agent, but is generally, for example, preferably in the range of 180 to 110 ° C, and more preferably in the range of 120 to 150 ° C. Can be implemented in
  • the above compound (1) is generally extracted into an organic phase in the range of acidic to weakly basic in the presence of an organic solvent and water.
  • the acidic to weakly basic range is usually from p HO to 9, preferably from pH 1 to 8.
  • Acids and / or bases can be used to adjust the extraction operation to acidic to weakly basic.
  • the acid and base are not particularly limited, but the acid is preferably a mineral acid such as hydrochloric acid or sulfuric acid, and the base is an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; sodium carbonate, carbonate Alkali metal carbonates such as sodium lime; sodium bicarbonate; and alkali metal bicarbonates such as hydrogen hydride.
  • the following compounds (7) are particularly novel compounds which have been found to be useful in the production of ⁇ -hydroxy-1 / 3-aminocarboxylic acid derivatives by the present inventors. Compound.
  • X 6 , X 7 and X 8 independently represent a bromine atom or a chlorine atom.
  • ⁇ 1 and ⁇ 2 each represent a hydrogen atom and the other represents a protecting group for an amino group. , Or together or each represents a protecting group for an amino group).
  • the halogenating agent is not particularly restricted but includes, for example, sulfuryl halides such as sulfuryl chloride; _-halosuccinimides such as ⁇ ⁇ -chlorosuccinimide and ⁇ ⁇ ⁇ -bromosuccinimide; halogens such as bromine and chlorine; iron chlorides and the like. Iron halide; hexacrocetone acetone and the like.
  • sulfuryl halides such as sulfuryl chloride
  • _-halosuccinimides such as ⁇ ⁇ -chlorosuccinimide and ⁇ ⁇ ⁇ -bromosuccinimide
  • halogens such as bromine and chlorine
  • iron chlorides and the like Iron halide
  • Iron halide hexacrocetone acetone and the like.
  • N-halosuccinimide such as N-chlorosuccinimide ⁇ N-bromosuccinimide is preferably used from the viewpoints of reaction development and simplicity
  • the equivalent of the halogenating agent is the type of the halogenating agent and 1 mole of the halogenating agent. Is determined by the halogenation ability of For example, when N-halosuccinimide is used, it can be used in an amount of about 1 to 5 mol, more preferably 1.1 to 3 mol, per 1 mol of hydrogen atom to be replaced with halogen.
  • the reaction solvent is not particularly limited, and examples thereof include hydrocarbons such as dichloromethane, chloroform, and toluene, and ethers such as tetrahydrofuran. It is preferable to use hydrocarbons, especially toluene, from the viewpoint of economy, safety and availability.
  • the reaction can be optionally performed in the presence of an acid or a base to accelerate the reaction.
  • an acid for example, when carrying out the reaction using sulfuryl peroxide, it is preferable to carry out the reaction in the presence of an acid.
  • the reaction is preferably carried out in the presence of a base.
  • the base may be a tertiary compound such as alkali metal carbonate such as potassium carbonate or triethylamine. It is preferable to use a base having relatively low nucleophilicity such as amine.
  • the type and amount of these acids and bases are not particularly limited, but can be easily optimized by simple experiments.
  • the reaction temperature must be appropriately determined according to the type of the halogenating agent. In general, the reaction is preferably carried out at 80 ° C. or lower, more preferably at room temperature or lower, in order to suppress side reactions such as excessive halogenation at other sites.
  • the following compound (6) is a novel compound which has been found by the present inventors to be useful in the production of ⁇ -hydroxy-aminocarboxylic acid derivatives. is there.
  • X 6 , X 7 and X s independently represent a bromine atom or a chlorine atom.
  • P 1 and P 2 each represent a hydrogen atom and the other represents a protecting group for an amino group. , Or together or each represents a protecting group for an amino group).
  • the compound (4) may be, for example, a reaction of an o; -haloacetic acid derivative or a salt thereof with an amino acid ester derivative (5) (WO 96/23756), or a dihalomethane and an amino acid ester derivative (WO 96/23756). It can be easily produced by the reaction of 5) (JP-A-8-234728).
  • (2 S, 3 S) contains 3.4 g (lmmo 1) of 1,1,1,1-trichloro-2-hydroxy-3-N- (ethoxycarbonyl) amino-4-phenylbutane
  • a 4N lithium hydroxide aqueous solution (22.5 g, 10 mmo 1)
  • the pH was adjusted to 0.7 with concentrated hydrochloric acid.
  • the organic phase was separated, the insolubles were removed by filtration, and the aqueous phase was concentrated under reduced pressure.
  • (2R, 3S) 1.5 g of an oil containing 1.2 g (0.6 mmo 1) of 2-hydroxy-3-amino-4-butyric acid was obtained.
  • solution B a solution comprising 6 g and 17.7 g of dimethoxyethane was prepared (this is referred to as solution B).
  • Solution A was added to solution B at an internal temperature of about 10 at an internal temperature of about 10 over 3 hours, and the reaction was further performed after 20 hours. Further, 100 g of water was added to another container, and the resulting reaction solution was added to the mixture while maintaining the pH at 1 to 7, and hydrolyzed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production de dérivés d'acide α-hydroxy-β-aminocarboxylique. Des dérivés de α-aminocétone (4) sont successivement halogénés, réduits et hydrolysés afin de produire efficacement des dérivés de α-amino-α', α', α'-trihalocétone (3), des dérivés de α-amino-α', α', α'-trihaloalcool (1) et des dérivés d'acide α-hydroxy-β-aminocarboxylique (2).
PCT/JP2001/006317 2000-07-26 2001-07-23 Procede de production de derives de $g(a)-amino-$g(a), $g(a)', $g(a)'-trihalocetone, de derives de $g(a)-amino-$g(a)', $g(a)', $g(a)'-trihaloalcool et de derives d'acide $g(a)-hydroxy-?-aminocarboxylique Ceased WO2002008170A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000225649A JP2002047256A (ja) 2000-07-26 2000-07-26 α−アミノ−α´，α´，α´−トリハロケトン誘導体、α−アミノ−α´，α´，α´−トリハロアルコ−ル誘導体、及び、α−ヒドロキシ−β−アミノカルボン酸誘導体の製造法
JP2000-225649 2000-07-26

Publications (1)

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WO2002008170A1 true WO2002008170A1 (fr) 2002-01-31

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009286778A (ja) * 2008-04-30 2009-12-10 Sumitomo Chemical Co Ltd ｔｅｒｔ−ブチル３−アミノピペリジン−１−カルボキシレートの製造方法およびその中間体
EP4545075A1 (fr) 2022-06-23 2025-04-30 Goryo Chemical, Inc. Inhibiteur de calpaïne

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2383156A1 (fr) * 1977-03-11 1978-10-06 Sagami Chem Res Derives de l'acide phenylacetique et procede de preparation
EP0341462A1 (fr) * 1988-05-11 1989-11-15 ZAMBON GROUP S.p.A. Procédé diastéréosélectif pour la préparation d'intermédiaires, utiles dans la synthèse de dérivés peptidiques
WO1992020357A1 (fr) * 1991-05-23 1992-11-26 Merrell Dow Pharmaceuticals Inc. Inhibiteurs de la cathepsine g et de l'elastase empechant la degradation du tissu conjonctif
US6020518A (en) * 1996-08-16 2000-02-01 Kaneka Corporation Process for preparing β-amino-α-hydroxy acid derivatives

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2383156A1 (fr) * 1977-03-11 1978-10-06 Sagami Chem Res Derives de l'acide phenylacetique et procede de preparation
EP0341462A1 (fr) * 1988-05-11 1989-11-15 ZAMBON GROUP S.p.A. Procédé diastéréosélectif pour la préparation d'intermédiaires, utiles dans la synthèse de dérivés peptidiques
WO1992020357A1 (fr) * 1991-05-23 1992-11-26 Merrell Dow Pharmaceuticals Inc. Inhibiteurs de la cathepsine g et de l'elastase empechant la degradation du tissu conjonctif
US6020518A (en) * 1996-08-16 2000-02-01 Kaneka Corporation Process for preparing β-amino-α-hydroxy acid derivatives

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