WO2021198888A1 - Réaction de carboxylation catalysée par une enzyme améliorée - Google Patents

Réaction de carboxylation catalysée par une enzyme améliorée Download PDF

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Publication number
WO2021198888A1
WO2021198888A1 PCT/IB2021/052602 IB2021052602W WO2021198888A1 WO 2021198888 A1 WO2021198888 A1 WO 2021198888A1 IB 2021052602 W IB2021052602 W IB 2021052602W WO 2021198888 A1 WO2021198888 A1 WO 2021198888A1
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Prior art keywords
aromatic
enzyme
ammonium
decarboxylase
carbonate
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PCT/IB2021/052602
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English (en)
Inventor
Pullela Venkata Srinivas
Parhalad Ray Sharma
Kandiraju Venkata Sita Ram RAO
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Pi Industries Ltd.
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Publication of WO2021198888A1 publication Critical patent/WO2021198888A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/42—Hydroxy-carboxylic acids

Definitions

  • the present invention relates to an improved process for the preparation of an aromatic hydroxy compound (Z), and salts thereof, using a decarboxylase enzyme. More particularly, an improved process for the preparation of 2,6-dihydroxybenzoic acid (Z 1 ) is provided by an enzyme catalyzed reaction using decarboxylase.
  • Phenolic acids such as hydroxybenzoic acids are important intermediates in the pharmaceutical and agrochemical industry.
  • a number of enzyme catalyzed regioselective ortho- or para-carboxyl ation reactions of aromatic hydroxy compounds have been reported in the literature.
  • Enzymes of the decarboxylase class are very useful for the synthesis of alcohols, carboxylic acids and other important chemicals. There are significant advantages in bio- carboxylation technology over synthetic techniques in terms of quality and quantity of the product.
  • Archives of Microbiology, 155 (1), 68-74 (1990) disclosed an anaerobic metabolism of resorcyclic acids. and resorcinol (1,3-benzenediol) in a fermenting co-culture of a Clostridium species with a Campylobacter species and other gram-negative bacterium.
  • Japanese patent application JP2001046093A disclosed a general method for producing a carboxylic acid of an aromatic alcohol by contacting the aromatic alcohol with a microorganism in the presence of carbonate ions or a carbon dioxide source (CO2); as depicted in the below Scheme-(l):
  • thermophilic, reversible g- resorcylate decarboxylase purified from Rhizobium species strain MTP- 10005, and utility of the enzyme as a reaction catalyst for the decarboxylation of 2,3- and 2,6-dihydroxybenzoate (resorcylate).
  • Japanese patent JP4414786 disclosed a method for producing 2,6-dihydroxy benzoic acid wherein the carbonic acid addition reaction is carried out under pressure reaction conditions in the presence of a 2,6-dihydroxy benzoic acid decarboxylase or a microbial strain such as Agrobacterium tumefaciens IAM 12048 strain having a 2,6-dihydroxy benzoic acid decarboxylase activity.
  • Rdc g— resorcylic acid decarboxylase
  • the present invention relates to the production of 2,6-dihydroxy benzoic acid decarboxylase by introducing recombinant pET-30 into the host cell, and subsequently the enzyme catalyzed carboxylation of aromatic hydroxy compound (Z), which is a chemical intermediate used for the preparation of various agrochemicals as well as pharmaceutical compounds. More particularly, the present invention relates to the carboxylation of aromatic hydroxy compound (Z 1 ) using 2,6-dihydroxy benzoic acid decarboxylase enzyme, wherein the enzyme is produced by incorporation of the recombinant pET-30 into the host cell such as Escherichia coli.
  • the process of the present invention does not involve the use of any toxic and/or costly solvents and reagents. Moreover, the process does not require a specified instrumental set up, additional purification steps and critical workup procedures. Accordingly, the present invention provides a process for the carboxylation of a substrate, which is simple, efficient, cost effective, environmentally friendly and commercially scalable for large scale operations.
  • the present invention relates to an improved process for the preparation of an aromatic hydroxy compound (Z) (as described herein), by contacting the decarboxylase enzyme with the substrate (A) in the presence of a carbonate ion or carbon dioxide (CO2) source; wherein the enzyme is produced by incorporation of the recombinant pET-30 into the host cell:
  • the present invention relates to an improved process for the preparation of an aromatic hydroxy compound (Z 1 ) (as described herein), by contacting the decarboxylase enzyme with the substrate (A 1 ) (as described herein) in the presence of a carbonate ion or carbon dioxide source (CO2); wherein the enzyme is produced by incorporation of the recombinant pET-30 into the host cell.
  • a carbonate ion or carbon dioxide source CO2
  • the present invention relates to an improved process for the preparation of 2,6-dihydroxy benzoic acid (Z 1 ) (as described herein), by contacting the 2,6-dihydroxy benzoic acid decarboxylase with the substrate (A 1 ) in the presence of carbonate ions or a carbon dioxide (CO2) source; wherein the enzyme is produced by incorporation of the recombinant pET-30a(+) into the host cell such as Escherichia coli.
  • Z 1 2,6-dihydroxy benzoic acid
  • CO2 carbon dioxide
  • the ‘host cell’ represents the bacterial cell wherein the recombinant plasmid vector is overexpressed.
  • the host cell can be selected from but is not limited to Escherichia coli, Aspergillus species, Comamonas and Bordetella strain, or Verminephrobacter strain.
  • the pET-30a-c(+) vectors carry an N-terminal His*Tag®/thrombin/S*TagTM/enterokinase configuration plus an optional C-terminal His*Tag sequence.
  • the sequence is numbered by the pBR322 convention, so the T7 expression region is reversed on the circular map.
  • the cloning/expression region of the coding strand transcribed by T7 RNA polymerase is shown below.
  • the fl origin is oriented so that infection with helper phage will produce virions containing single-stranded DNA that corresponds to the coding strand. Therefore, single-stranded sequencing should be performed using the T7 terminator primer:
  • A the substrate
  • CO2 carbon dioxide source
  • D is a carbocycle, heterocycle, aryl, heteroaryl, aromatic or hetero- aromatic ring, mono or bicyclic aromatic, mono or bicyclic hetero -aromatic groups, as defined herein, are optionally substituted (e.g., "substituted” or “unsubstituted” carbocyclyl, "substituted” or “unsubstituted” heterocyclyl, "substituted” or “unsubstituted” aryl or “substituted” or “unsubstituted” heteroaryl group).
  • substituted means that at least one hydrogen present on a group (e.g., a carbon or nitrogen atom etc.) is replaced with a permissible substituent, e.g., a substituent which upon substitution results in a stable compound.
  • a "substituted” group has a substituent at one or more substitutable positions of the group, and when more than one position in any given structure is substituted, the substituent is either the same or different at each position.
  • carrier includes "aromatic carbocyclic ring system” and “nonaromatic carbocylic ring system” or polycyclic or bicyclic (spiro, fused, bridged, nonfused) ring compounds in which ring may be aromatic or non-aromatic (where aromatic indicates that the Huckel rule is satisfied and non-aromatic indicates that the Huckel rule is not statisfied).
  • hetero in connection with rings refers to a ring in which at least one ring atom is not carbon and which can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.
  • aromatic indicates that the Huckel rule is satisfied and the term “non- aromatic” indicates that the Huckel rule is not satisfied.
  • non-aromatic heterocycle or “non-aromatic heterocyclic” means three- to fifteen- membered, preferably three- to twelve-membered, saturated or partially unsaturated heterocycle containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur: mono, bi- or tricyclic heterocycles which contain, in addition to carbon ring members, one to three nitrogen atoms and/or one oxygen or sulphur atom or one or two oxygen and/or sulphur atoms; if the ring contains more than one oxygen atom, they are not directly adjacent; for example (but not limited to) oxetanyl, oxiranyl, aziridinyl, thietanyl, 2- tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3 -tetrahydro thienyl, 1- pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 1- pyr
  • heteroaryl or "aromatic heterocyclic” means 5 or 6-membered, fully unsaturated monocyclic ring system containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur; if the ring contains more than one oxygen atom, they are not directly adjacent; 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom as ring members, for example (but not limited thereto) furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl,
  • 6-membered heteroaryl groups which contains one to four nitrogen atoms 6-membered heteroaryl groups which, in addition to carbon atoms, may contain, respectively, one to three and one to four nitrogen atoms as ring members, for example (but not limited thereto) 2- pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4- pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, l,3,5-triazin-2-yl, l,2,4-triazin-3-yl and 1,2, 4, 5- tetrazin-3-yl; benzofused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom: for example (but not limited to) indol-1- yl, indol-2-yl, indol-3-yl, indol-4-
  • Bicyclic 5-6 heteroaryl systems with one bridgehead (Ring Junction) nitrogen atom containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom for example (but not limited to) imidazo[l,2-a]pyridine, imidazo[l,2-a]pyrimidine, [l,2,4]triazolo[l,5-a]pyrimidine, [l,2,4]triazolo[l,5-b]pyridazine, [l,2,4]triazolo[l,5- ajpyrazinc, [l,2,4]triazolo[l,5-a]pyridine, imidazo[l,2-c]pyrimidine, imidazo[l,2- b]pyridazine, [l,2,4]triazolo[l,5-c]pyrimidine, 1 -methyl- lH-indole, imidazo[l,2-a]pyrazine, pyrazolo[l,5
  • aryl further comprises “arylsulfyl” includes Ar-S(O), wherein Ar can be any carbocyle or heterocylcle.
  • Ar can be any carbocyle or heterocylcle.
  • alkylsulphinyl as a part of a composite substituent, for example haloalkylsulphinyl etc., unless specifically defined elsewhere.
  • alkylsulfonyl include but are not limited to methylsulphonyl, ethylsulphonyl, propylsulphonyl, 1-methylethylsulphonyl, butylsulphonyl, 1- methylpropylsulphonyl, 2-methylpropylsulphonyl, 1,1 -dimethyl ethylsulphonyl, pentylsulphonyl, 1-methylbutylsulphonyl, 2- methylbutylsulphonyl, 3-methylbutylsulphonyl, 2,2-dimethylpropylsulphonyl, 1-ethylpropylsulphonyl, hexylsulphonyl, 1,1- dimethylpropylsulphonyl, 1,2-dimethylpropylsulphonyl, 1-methylpentylsulphonyl, 2- methylpentylsulphonyl, 3-methylpentyls
  • arylsulfonyl includes Ar-S(0) 2 , wherein Ar can be any carbocyle or heterocylcle. This definition also applies to alkylsulphonyl as a part of a composite substituent, for example alkylsulphonylalkyl etc., unless defined elsewhere.
  • bicyclic ring or ring system denotes a ring system consisting of two or more common atoms.
  • aromatic indicates that the Hueckel rule is satisfied and the term “non-aromatic” indicates that the Hueckel rule is not satisfied.
  • carrier or “carbocyclic” or “carbocyclyl” include “aromatic carbocyclic ring system” and “nonaromatic carbocylic ring system” or polycyclic or bicyclic (spiro, fused, bridged, nonfused) ring compounds in which the ring may be aromatic or non-aromatic (where aromatic indicates that the Huckel rule is satisfied and non-aromatic indicates that the Huckel rule is not satisfied).
  • aryl as used herein is a group that contains any carbon-based aromatic group including, but not limited to phenyl, naphthalene, biphenyl, anthracene, and the like. The aryl group can be substituted or unsubstituted.
  • the aryl group can be a single ring structure or comprise multiple ring structures that are either fused ring structures or attached via one or more bridging groups such as a carbon-carbon bond.
  • aryl also comprises “aralkyl” refers to aryl hydrocarbon radicals including an alkyl portion as defined above. Examples include benzyl, phenylethyl, and 6-napthylhexyl.
  • aralkenyl refers to aryl hydrocarbon radicals including an alkenyl portion, as defined above, and an aryl portion, as defined above. Examples include styryl, 3- (benzyl) prop-2-enyl, and 6-napthylhex-2-enyl.
  • hetero in connection with rings refers to a ring in which at least one ring atom is not carbon and which can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.
  • heteroaryl as a part of a composite substituent, for example heteroarylalkyl etc., unless specifically defined elsewhere.
  • any of the compounds according to the invention can also exist in one or more geometric isomer forms depending on the number of double bonds, chiral center or geometric rearrangement in the compound.
  • the invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions.
  • the geometric isomers can be separated according to general methods, which are known per se by a person ordinary skilled in the art.
  • the process of the present invention as per a general embodiment relates to an improved process for the preparation of an aromatic hydroxy compound (Z) (as described herein), using a decarboxylase enzyme as a catalyst is illustrated in the following Scheme-(I): decarboxylase
  • the present invention relates to an improved process for the preparation of an aromatic hydroxy compound (Z 1 ) or a salt thereof; represented by the formula: comprising the step of contacting the decarboxylase enzyme with the substrate (A 1 ), represented by the formula: in the presence of carbonate ions or a carbon dioxide (CO2) source; wherein the enzyme is produced by incorporation of the recombinant pET-30 into the host cell.
  • the source of carbonate ions or the carbon dioxide (CO2) source is selected from but is not limited to carbon dioxide gas (CO2), potassium bicarbonate (KHCO 3 ), ammonium carbonate (NH 4 CO 3 ), ammonium bicarbonate (NH 4 HCO 3 ), sodium bicarbonate (NaHCCE), potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 C0 3 ).
  • the product formed was precipitated by adding suitable quaternary ammonium salts.
  • the source of a suitable quaternary ammonium salt is selected from but is not limited to the tetra-butyl ammonium bromide, tetra-butyl ammonium chloride, tetra-butyl ammonium fluoride, dodecyltrimethyl ammonium chloride, tetrabutylammonium hydrogensulfate.
  • the suitable solvent is selected from but is not limited to protic solvents, polar aprotic solvents and nonpolar solvents, including aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters, ketones, amides, water or mixtures thereof.
  • the product formed was precipitated by adding suitable acids selected from but not limited to inorganic acids (e.g. hydrochloric acid, hydrobromic acid, sulfuric acid, etc.), organic acids (e.g. formic acid, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid).
  • suitable acids selected from but not limited to inorganic acids (e.g. hydrochloric acid, hydrobromic acid, sulfuric acid, etc.), organic acids (e.g. formic acid, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid).
  • said enzyme is produced by incorporation of the recombinant pET-30 into the host cell such as Escherichia coli.
  • the process may optionally be carried out in the presence of a suitable buffer selected from but not limited to sodium hydrogen phosphates (NathPCE , NaiHPC ), potassium hydrogen phosphates (KH 2 PO 4 , K 2 HPO 4 ), potassium bicarbonate (KHCO 3 ), ammonium carbonate (NH 4 CO 3 ), ammonium bicarbonate (NH 4 HCO 3 ), sodium bicarbonate (NaHCOi), sodium bisulphite (NaHSCh), ammonium chloride (NH 4 CI).
  • a suitable buffer selected from but not limited to sodium hydrogen phosphates (NathPCE , NaiHPC ), potassium hydrogen phosphates (KH 2 PO 4 , K 2 HPO 4 ), potassium bicarbonate (KHCO 3 ), ammonium carbonate (NH 4 CO 3 ), ammonium bicarbonate (NH 4 HCO 3 ), sodium bicarbonate (NaHCOi), sodium bisulphite (NaHSCh), ammonium chloride (NH 4
  • the present invention relates to an improved process for the preparation of 2,6-dihydroxy benzoic acid (Z 1 ) as depicted in the below Scheme-(II), by contacting the 2,6-dihydroxy benzoic acid decarboxylase with the substrate (A 1 ) in the presence of carbonate ions or a carbon dioxide (CO2) source; wherein the enzyme is produced by incorporation of the recombinant pET-30a(+) into the host cell such as Escherichia coli.
  • Scheme-(II) The process as illustrated in the above scheme-(II) comprises dissolving the compound (A 1 ) in a solvent, followed by its treatment with 2,6-dihydroxy benzoic acid decarboxylase enzyme in the presence of potassium bicarbonate (KHCO3). The reaction mass was filtered off and the desired product was isolated with a yield of more than 80% and a purity of > 99% (HPLC). In one embodiment, the yield of the aromatic hydroxy compound (Z) is in the range of 70 to 98%.
  • the purity of the aromatic hydroxy compound (Z) is in the range of 90 to 99%.
  • the 2,6-dihydroxy benzoic acid decarboxylase (2,6-DHBD) producing gene sequences from Rhizobium sporomusa (MTP- 10005 - 984 bp), Rhizobium radiobacter WU-0108 or Agrobacterium tumefaciens (984 bp) were synthesized and ligated into a pET-30a-c(+) vector.
  • the obtained plasmids were transformed in a standard Escherichia coli host (BL21) for overexpression.
  • the 984 bp amino acid sequence corresponds to the 2,6-dihydroxybenzoic acid decarboxylase depicted below: gaccgaggagcttcagcgttgcgtcaacgatctcggtttcgtcggcgcgctcgtcaacggcttcagccaggagggcgat ggccagacaccgctatattacgacctgccgcaatatcgtccattctggggcgaggtggaaaagcttgatgtgcctttctatc tgcatcccgcgctaccgcaggattcccgcatctatgacggccacccctggctgcttggccccacctgggcgtttgcgtttg cgcaggaaacggcggttcacgctcatggcatcaggcatcaggctatgacggc
  • the solvent used during any step of the process is selected from but is not limited to halogenated solvents such as dichloromethane, 4- bromotoluene, diiodomethane, carbon tetrachloride, chlorobenzene and chloroform; alcoholic solvent such as methanol, ethanol, isopropanol, t-amyl alcohol, t-butyl alcohol and hexanol; an ether solvent such as tetrahydrofuran, cyclopentyl methyl ether, 2-methyltetrahydrofuran, diethyl ether and 1,4-dioxane; a ketone selected from methyl ethyl ketone, acetone; an aprotic solvent such as acetonitrile, N,N-dimethyl formamide (DMF), N,N-dimethyl acetamide, dimethyl sulfoxide (DMSO) and N
  • halogenated solvents such as dichloromethane, 4- bro
  • the carboxylation reaction of the present invention can be carried out in closed vessel e.g autoclave.
  • the carboxylation reaction is optionally performed under pressure condition.
  • the product obtained from the process as depicted in Scheme-(I) or (II) is isolated from the reaction mixture, and corresponds to any of the steps involving biphasic separation, separation of organic phase, filtration, evaporation of solvent, cooling, precipitation, washing and drying.
  • the 2,6-DHBD enzyme is immobilized.
  • immobilized when used in reference to any element; including a process step or a product e.g. immobilized enzyme; is intended to mean the immobilization of the enzyme on an appropriate inert support material.
  • the method of formation of immobilized enzyme may comprises grafting, physical adsorption, ion-pair formation, and entrapment.
  • the present invention relates to the use of an immobilized enzyme as a catalyst for carboxylation reactions; wherein the immobilized enzyme is repeatedly used for hydrogenation reactions without any activation and the enzyme is produced by incorporation of the recombinant pET-30a(+) into the host cell such as Escherichia coli.
  • DHBA 2,6-dihydroxybenzoic acid
  • Rhizobium sporomusa 2,6-DHBD Rs
  • the genes were ligated suitably into a pET vector specifically pET30a (+).
  • the obtained plasmids were transformed to an E. coli host specifically BL21 (DE3) for over expression.
  • the over expression of enzyme was performed as follows:
  • the pre-inoculum was prepared in a 50 mL medium containing Tryptone, sodium chloride, and yeast extract supplemented with appropriate antibiotics such as kanamycin (20- 80pg/mL).
  • the pre-inoculum was inoculated and incubated at 37°C for 16 h in an incubatory shaker.
  • About 0.5-1% v/v of the pre-inoculum was inoculated into 400 mL medium of above said media composition and incubated in an incubatory shaker until an optical density (OD 600) of 0.6-1.0 was reached.
  • IPTG Isopropyl b- D-l-thiogalactopyranoside
  • Example-1 Production of enzyme: 2,6-dihydroxy benzoic acid decarboxylase The overexpression of enzyme was performed as follows:
  • pre-inoculum 50 ruL Luria Bertani medium supplemented with appropriate antibiotics [kanamycin (50 pg/mL)] 2,6-DHBD were inoculated and incubated at 37 ° C and 180 rpm for 16 h to obtain pre-inoculum.
  • 1% v/v of the pre-inoculum culture was inoculated into 400 ruL Luria Bertani medium containing kanamycin (50 pg/mL) until an optical densistydensity (OD 600) of 0.6- 1.0 was reached.
  • InM IPTG was added for induction and the cells were left overnight at 20°C and 120 rpm.
  • the culture was harvested by centrifugation at 5,000 - 8,000 rpm for 10 min to obtain a cell pellet which was used for carboxylation.

Abstract

La présente invention concerne un procédé amélioré pour la préparation d'un composé hydroxy aromatique (Z) (tel que décrit ici), et des sels de celui-ci, à l'aide d'une enzyme décarboxylase. Plus particulièrement, il est fourni un procédé amélioré pour la préparation de l'acide 2,6-dihydroxybenzoïque (Z1) (tel que décrit ici) par une réaction catalysée par une enzyme utilisant la décarboxylase, dans lequel l'enzyme est produite par incorporation du pET-30a(+) recombiné dans une cellule hôte telle que Escherichia coli.
PCT/IB2021/052602 2020-03-31 2021-03-30 Réaction de carboxylation catalysée par une enzyme améliorée WO2021198888A1 (fr)

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JPS5126808B1 (fr) 1967-11-14 1976-08-09
JP2001046093A (ja) 1999-08-11 2001-02-20 Mitsui Chemicals Inc 多価アルコール芳香族カルボン酸の製造方法
WO2005054462A1 (fr) 2003-11-11 2005-06-16 Mitsui Chemicals, Inc. 2,6 dihydroxybenzoate decarboxylase thermotolerante et procede de production d'acide 2,6 dihydroxybenzoique
JP4414786B2 (ja) 2004-03-04 2010-02-10 国立大学法人岐阜大学 ２，６−ジヒドロキシ安息香酸脱炭酸酵素タンパク質をコードするｄｎａ及びこれを利用した多価アルコ−ル芳香族カルボン酸の製造方法
JP4719535B2 (ja) 2005-09-01 2011-07-06 国立大学法人岐阜大学 ２，６−ジヒドロキシ安息香酸脱炭酸酵素、その酵素をコードするポリヌクレオチド、その製造方法、およびこれを利用した多価アルコ−ル芳香族化合物の製造方法
WO2013023999A1 (fr) 2011-08-12 2013-02-21 Acib Gmbh Carboxylation régiosélective de composés de substrats non naturels par l'utilisation de décarboxylases

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Publication number Priority date Publication date Assignee Title
JPS5126808B1 (fr) 1967-11-14 1976-08-09
JP2001046093A (ja) 1999-08-11 2001-02-20 Mitsui Chemicals Inc 多価アルコール芳香族カルボン酸の製造方法
WO2005054462A1 (fr) 2003-11-11 2005-06-16 Mitsui Chemicals, Inc. 2,6 dihydroxybenzoate decarboxylase thermotolerante et procede de production d'acide 2,6 dihydroxybenzoique
JP4414786B2 (ja) 2004-03-04 2010-02-10 国立大学法人岐阜大学 ２，６−ジヒドロキシ安息香酸脱炭酸酵素タンパク質をコードするｄｎａ及びこれを利用した多価アルコ−ル芳香族カルボン酸の製造方法
JP4719535B2 (ja) 2005-09-01 2011-07-06 国立大学法人岐阜大学 ２，６−ジヒドロキシ安息香酸脱炭酸酵素、その酵素をコードするポリヌクレオチド、その製造方法、およびこれを利用した多価アルコ−ル芳香族化合物の製造方法
WO2013023999A1 (fr) 2011-08-12 2013-02-21 Acib Gmbh Carboxylation régiosélective de composés de substrats non naturels par l'utilisation de décarboxylases

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