WO2014014035A1 - Composé d'ester d'acide pyrophosphorique, composé d'ester d'acide biphosphorique, et catalyseur - Google Patents

Composé d'ester d'acide pyrophosphorique, composé d'ester d'acide biphosphorique, et catalyseur Download PDF

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WO2014014035A1
WO2014014035A1 PCT/JP2013/069443 JP2013069443W WO2014014035A1 WO 2014014035 A1 WO2014014035 A1 WO 2014014035A1 JP 2013069443 W JP2013069443 W JP 2013069443W WO 2014014035 A1 WO2014014035 A1 WO 2014014035A1
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石原　一彰
彰 坂倉
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国立大学法人名古屋大学
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    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
    • B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, 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
    • 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
    • B01J31/1845—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 phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
    • 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
    • C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B01J2231/346—Mannich type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues to aldimines or ketimines
    • 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
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • 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
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/68—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/73—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom of a carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups

Definitions

  • the present invention relates to a novel pyrophosphate ester compound, a bisphosphate ester compound and a catalyst.
  • Patent Document 1 3,3′-diaryl-1,1′-binaphthyl-2,2′-diyl hydrogen phosphate, which is a phosphate ester compound, is converted into Mannich reaction, hydrophosphorylation reaction, aza diels alder reaction. It is used as a catalyst.
  • the present invention has been made to solve such problems, and has as its main object to provide a novel pyrophosphate ester compound and bisphosphate ester compound.
  • the present inventors have reacted sodium hydride and diallyl phosphate with a BINOL derivative having a substituent at the 3,3 ′ position (BINOL is an abbreviation for 1,1′-bi-2-naphthol).
  • BINOL is an abbreviation for 1,1′-bi-2-naphthol.
  • a novel bisphosphate compound was obtained.
  • the novel pyrophosphate ester compound was obtained by making this bisphosphate ester compound react with oxalyl chloride.
  • the intramolecular ene reaction or Mannich reaction was carried out using the novel pyrophosphate ester compound or bisphosphate ester compound thus obtained as a catalyst, the activity was higher than in the case where a conventional phosphate ester compound was used as the catalyst. This was confirmed and the present invention was completed.
  • the pyrophosphate ester compound of the present invention is represented by the formula (1).
  • R is an aryl group, an organic silyl group, or a halogen atom.
  • the bisphosphate compound of the present invention is represented by the formula (2).
  • R is an aryl group, an organic silyl group, or a halogen atom.
  • novel pyrophosphate ester compound and bisphosphate ester compound of the present invention have a plurality of phosphate hydroxyl groups in the molecule, the acidity is higher than that of conventional phosphate ester compounds. Therefore, the ability to activate carbonyl compounds and imine compounds is high. In addition, it is expected to be useful as a ligand. Furthermore, since it has a binaphthyl skeleton, it can be a chiral pyrophosphate ester compound or bisphosphate ester compound.
  • the pyrophosphate ester compound of the present invention is represented by the above formula (1), and R is an aryl group, an organic silyl group or a halogen atom.
  • the bisphosphate compound of the present invention is represented by the above formula (2), and R is an aryl group, an organic silyl group, or a halogen atom.
  • examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.
  • the naphthyl group may be a 1-naphthyl group or a 2-naphthyl group.
  • the anthracenyl group may be a 1-anthracenyl group, a 2-anthracenyl group, or a 9-anthracenyl group.
  • at least one hydrogen atom may be substituted with a substituent.
  • substituents examples include an aryl group, an alkyl group, a cycloalkyl group, an alkoxy group, a perfluoroalkyl group, a nitro group, a cyano group, and a halogen atom.
  • aryl group in addition to a phenyl group, a naphthyl group, an anthracenyl group, etc., at least one of these hydrogen atoms is substituted with an alkyl group, an alkoxy group, a perfluoroalkyl group, a nitro group, a cyano group, a halogen atom, or the like. It may be.
  • Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.
  • Examples of the perfluoroalkyl group include a trifluoromethyl group and a pentafluoroethyl group.
  • Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
  • Such an aryl group is particularly preferably a 2-naphthyl group, a 3,5-diphenylphenyl group or a 3,5-bis (2-naphthyl) phenyl group.
  • Examples of the organic silyl group include a trialkylsilyl group, a triarylsilyl group, an alkyldiarylsilyl group, an aryldialkylsilyl group, a tris (trialkylsilyl) silyl group, and a tris (triarylsilyl) silyl group.
  • a trialkylsilyl group all three alkyl groups may be the same, two may be the same, or all may be different.
  • the triarylsilyl group all three aryl groups may be the same, two may be the same, or all may be different.
  • In the alkyldiarylsilyl group two aryl groups may be the same or different.
  • two alkyl groups may be the same or different.
  • the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, diethylisopropylsilyl group, dimethylisopropylsilyl group, di-tert-butylmethylsilyl group, isopropyldimethylsilyl group, tert-butyldimethylsilyl group. Group and the like.
  • the triarylsilyl group include a triphenylsilyl group.
  • Examples of the alkyldiarylsilyl group include a diphenylmethylsilyl group and a tert-butyldiphenylsilyl group.
  • Examples of the aryldialkylsilyl group include a dimethylphenylsilyl group.
  • Examples of the tris (trialkylsilyl) silyl group include a tris (trimethylsilyl) silyl group.
  • Examples of the tris (triarylsilyl) silyl group include a tris (triphenylsilyl) silyl group.
  • halogen atom examples include a chlorine atom, a bromine atom, and an iodine atom.
  • the production method of the pyrophosphate ester compound and bisphosphate ester compound of the present invention is not particularly limited, but an example is shown below. That is, for example, a bisphosphate compound is prepared by reacting a BINOL derivative having a substituent R (R is as described above) at the 3,3′-position with sodium hydride and diallyl chloride and then protecting allyl. It can be obtained by removing the group.
  • the pyrophosphate ester compound can be obtained, for example, by reacting the bisphosphate ester compound described above with oxalyl chloride.
  • the use of the pyrophosphate ester compound and bisphosphate ester compound of the present invention is not particularly limited, and examples thereof include reaction catalysts and ligands.
  • it can be used as a catalyst for intramolecular ene reaction of 6-octenal derivatives (such as citronellal), a Mannich reaction catalyst, and a Friedel-Crafts reaction catalyst.
  • 6-octenal derivatives such as citronellal
  • Mannich reaction catalyst such as citronellal
  • Friedel-Crafts reaction catalyst a Friedel-Crafts reaction catalyst.
  • a chiral pyrophosphate ester compound or a chiral bisphosphate ester compound can be easily obtained. Such chiral compounds are expected to be used as catalysts for asymmetric synthesis reactions.
  • the bisphosphate compound is also useful as a synthesis intermediate for pyrophosphate compounds.
  • Example 1 60% sodium hydride mineral oil dispersion (0.89 g, 22 mmol) was added to a solution of (R) -3,3′-diphenylBINOL (4.4 g, 10 mmol) in THF (50 mL) at 0 ° C. and stirred for 30 minutes. did. To this solution, diallyl phosphoric acid chloride (7.8 g, 40 mmol) was added and stirred at room temperature for 2 hours. Water was added to the reaction mixture and the mixture was extracted with dichloromethane. The organic layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate.
  • diallyl phosphoric acid chloride 7.8 g, 40 mmol
  • Example 2 instead of (R) -3,3′-diphenyl BINOL used in Example 1, (R) -3,3′-bis [4- (2,4,6-trimethylphenyl) phenyl] BINOL was used. Except for the above, a bisphosphate compound (Compound B2) was obtained in the same manner as in Example 1.
  • the spectrum data is as follows.
  • Example 3 Except for using (R) -3,3′-bis [3,5-bis (trifluoromethyl) phenyl] BINOL instead of (R) -3,3′-diphenyl BINOL used in Example 1. In the same manner as in Example 1, a bisphosphate compound (Compound B3) was obtained.
  • the spectrum data is as follows.
  • the synthesis procedure of compounds B11 and B12 will be described below.
  • the first stage reaction was carried out according to Example 1. However, since the substituent at the 3,3′-position is bulky, only one phosphate group was introduced.
  • the reaction after the second stage was performed as follows. To the THF solution of the first stage reaction product, triethylamine (4 equivalents) is added, cooled to 0 ° C., phosphorus trichloride (1.2 equivalents) is added, and then the temperature is raised to room temperature for 10 minutes. Stir. The mixed solution was cooled again to 0 ° C., allyl alcohol (4 equivalents) was added, the temperature was raised to room temperature, and the mixture was stirred for 30 minutes.
  • Example 4 After adding oxalyl chloride (0.030 mL, 0.35 mmol) to a solution of BINOL bisphosphate (Compound B 1,62 mg, 0.10 mmol) and DMF (0.010 mL) in dichloromethane (1.0 mL) at room temperature, The mixture was heated to 40 ° C. and stirred for 30 minutes. The reaction mixture was concentrated under reduced pressure to obtain the desired BINOL pyrophosphate ester (Compound A1, 5.9 mg, 100%). The structure of this pyrophosphate ester was determined by measuring NMR spectrum and mass spectrum. The spectrum data is as follows.
  • Example 5 A pyrophosphate ester compound (Compound A2) was obtained in the same manner as in Example 4 except that Compound B2 was used instead of Compound B1 used in Example 4.
  • Example 6 A pyrophosphate ester compound (Compound A3) was obtained in the same manner as in Example 4 except that Compound B3 was used instead of Compound B1 used in Example 4.
  • Table 1 shows the reaction conditions. From Table 1, it can be seen that when the compounds A1 to A3 are used as the catalyst, the activity is considerably higher than when the compound C is used as the catalyst.
  • Intramolecular ene reaction (part 2) Intramolecular ene reaction was carried out in the same manner as in 3-1, except that 3,3,7-trimethyl-6-octenal was used in place of citronellal in 3-1. The results are shown in Table 2. Table 2 also shows the reaction conditions. As is apparent from Table 2, compounds A1 to A3 showed excellent catalytic activity, whereas when compound C was used as a catalyst, almost no product was obtained. When the reaction temperature was ⁇ 78 ° C., the catalytic activities of the compounds A2 and A3 were higher than that of the compound A1. From this, it was suggested that when the phenyl group having a substituent is bonded to the 3,3′-position of BINOL, a higher catalytic activity is exhibited when the phenyl group having a substituent is bonded. .
  • N-benzyloxycarbonyl (Cbz) aldimine (2 mmol) was dissolved at room temperature in a methylene chloride solution (1 mL) of compound A1 (0.01 mmol) prepared immediately before the o-cresol (3 mmol) chloride. Methylene solution was added at 0 ° C. and stirred for 3 hours. Water (2 mL) was added to the reaction solution to stop the reaction, followed by liquid separation with ethyl acetate, and the solvent was removed under reduced pressure.
  • the spectral data of this product is as follows.
  • entry 4 in Table 5 the reaction was performed in the same manner as in entry 1 except that the concentration of entry 1 in Table 5 was changed to 10 mM. As a result, the enantioselectivity improved to 81% ee, and the yield also improved to 97%. Furthermore, in entry 5 of Table 5, the reaction was performed in the same manner as in entry 4 except that the amount of catalyst used in entry 4 of Table 5 was changed to 1 mol%. As a result, even if the amount of the catalyst used was 1 mol%, it showed a high enantioselectivity of 79% ee. In entries 4 and 5 of Table 5, N-methoxycarbonylaldimine was used in an amount equivalent to 1.5 equivalents of o-cresol, and the amount of catalyst used, concentration, and yield were calculated based on o-cresol.
  • the present invention is mainly applicable to the chemical industry, and can be used, for example, in the production of pharmaceuticals, agricultural chemicals, cosmetics, and intermediates thereof, or can be used as a metal ligand.

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Abstract

Cette invention concerne un nouveau composé d'ester d'acide pyrophosphorique représenté par la formule (1), et un composé d'ester d'acide biphosphorique représenté par la formule (2). Dans les formules, R est un groupe aryle, un groupe silyle organique, ou un atome d'halogène. Ces composés peuvent activer de manière adéquate des composés carbonyle, des composés imine, et autres en raison de leur acidité supérieure à celle des composés d'ester d'acide phosphorique classiques. Les composés selon l'invention devraient également être utiles à titre de ligand métallique.
PCT/JP2013/069443 2012-07-19 2013-07-17 Composé d'ester d'acide pyrophosphorique, composé d'ester d'acide biphosphorique, et catalyseur WO2014014035A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP2016098207A (ja) * 2014-11-25 2016-05-30 高砂香料工業株式会社 光学活性アルコールの製造方法
CN116041221A (zh) * 2023-01-17 2023-05-02 上海市奉贤区中心医院 一种合成手性二芳基甲胺衍生物的方法

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JPS5069090A (en) * 1973-03-29 1975-06-09 Univ California Shinki na maruchiheterokyodaikankagobutsu no seiho
WO2004096753A1 (fr) * 2003-04-25 2004-11-11 Toagosei Co., Ltd. Catalyseur de synthese asymetrique a base d'acide de bronsted chiral et procede de synthese asymetrique avec ce catalyseur
JP2006035125A (ja) * 2004-07-28 2006-02-09 Japan Science & Technology Agency 不斉触媒、光学活性アルコールの製造方法及びビナフトール誘導体
WO2007114445A1 (fr) * 2006-04-04 2007-10-11 Kuraray Co., Ltd. Procédé de production d'aldéhyde à l'aide de bisphosphite et d'un composé métallique des groupes 8 à 10, et bisphosphite
WO2011111677A1 (fr) * 2010-03-09 2011-09-15 国立大学法人東北大学 Bisphosphate et réaction asymétrique l'employant

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