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WO2002012171A1 - Procede de preparation de composes chiraux par des reactions d'ouverture de cycle asymetrique d'epoxydes - Google Patents

Procede de preparation de composes chiraux par des reactions d'ouverture de cycle asymetrique d'epoxydes Download PDF

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WO2002012171A1
WO2002012171A1 PCT/KR2001/000597 KR0100597W WO0212171A1 WO 2002012171 A1 WO2002012171 A1 WO 2002012171A1 KR 0100597 W KR0100597 W KR 0100597W WO 0212171 A1 WO0212171 A1 WO 0212171A1
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formula
group
alkyl
chiral
catalyst
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PCT/KR2001/000597
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Choong-Eui Song
Eun-Joo Roh
Chun-Rim Oh
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Korea Institute Of Science And Technology
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Application filed by Korea Institute Of Science And Technology filed Critical Korea Institute Of Science And Technology
Priority to AU2002229148A priority Critical patent/AU2002229148A1/en
Publication of WO2002012171A1 publication Critical patent/WO2002012171A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C247/04—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/14—Compounds containing azido groups with azido groups bound to carbon atoms of rings other than six-membered aromatic rings
    • 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
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
    • C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • 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
    • C07C2601/14—The ring being saturated
    • 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
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method for preparing chiral compounds by the asymmetric ring opening reactions of epoxides, more particularly, to a method preparing chiral compounds by means of asymmetric ring opening reactions of epoxides with nucleophiles in the presence of a salt followed formula 1 and chiral salen metallic catalysts.
  • Such a method facilitates recovery and reuse of the expensive catalyst in which the catalyst maintains its activity and enantioselectivity, such that chiral compounds can be prepared m an economic manner.
  • Formula 1 Formula 1
  • R 1 , R 2 , R 3 , R 4 , X, Z, n and Y are as defined in the description.
  • Production methods of chiral compounds in current use can be classified into two groups: one taking advantage of chiral pools and the other using optical resolution.
  • chiral compounds can be prepared through the asymmetric ring-opening reaction of racemic or meso epoxides (E. N. Jacobsen and M. H. Wu, Ring Opening of Epoxides and Related Reactions r in Comprehensive Asymmetric Catalysis III, ed. E. N. Jacobsen, A. Pfaltz and H. Yamamoto, Springer Verlag, Berlin-Heidelberg-New York, 1999, p. 1309) . (Reaction Scheme 1)
  • the asymmetric ring opening of epoxides are conducted with nucleophiles in the presence of a chiral salen catalyst so as to produce chiral compounds with various functional groups.
  • useful nucleophiles include N 3 ⁇ , NH 3 , H 2 NR, HNR 2 , H 2 0, ROH, PhOH, RSH, H " , RCH 2 " , etc.
  • a variety of chiral salen catalysts are usefully utilized [E. N. Jacobsen and M. H. Wu, Ring Opening of Epoxides and Related Reactions,, in Comprehensive Asymmetric Ca talysis III, ed. E. N. Jacobsen, A.
  • chiral salen catalysts are used to synthesize chiral epoxides through asymmetric epoxidation.
  • Chiral salen catalysts although being used for both asymmetric ring opening reactions and epoxidation, can be distinguished from each other depending on the reactions for which they are used.
  • chiral salen catalysts comprise Mn as a catalytically effective metal when they are used for epoxidation, while comprising Cr or Co as a catalytically effective metal for asymmetric ring opening reactions [US 5,637,739 (1997), US 5,663,393 (1997), US 5,420,314 (1995), US 5,599,957 (1997), WO 93/03838 (1993) and WO 94/03271 (1994), US 5,352,814 (1994), US 5,639,889 (1997) and US 5,916,975 (1999)] .
  • kinetic resolution is to react a nucleophile with one enantiomer in the presence of a chiral catalyst to afford various chiral compounds.
  • a chiral catalyst For instance, where water is used as a nucleophile for racemic epoxides, one enantiomer is opened by water to produce chiral diols, which are very important intermediates that can find numerous applications in various fine chemical industries.
  • the other epoxide enantiomer is not reacted with the nuclephile and thus remains as it is [Tokunaga, M. ; Larrow, J. F.; Kakiuchi, F.; Jacobsen, E., Science, 1997, 277, 936] .
  • the asymmetric ring opening reactions of epoxides using chiral salen catalysts can be broken down into the kinetic resolution of racemic epoxides and the enantioselective ring opening reaction of meso epoxides.
  • the asymmetric ring opening of racemic or meso epoxides is difficult to apply to industrial fields because the chiral salen catalysts used are prepared under intricate reaction conditions by multi-step processes, in addition to being very expensive.
  • epoxides are reacted with nucleophiles in the presence of a chiral salen catalyst in a solvent containing only a salt represented by the following formula 1 alone or in combination with other solvent components, and the catalyst can be reused while remaining the solvent without a decrease in its catalytic activity and enantiselectivity.
  • the present invention relates to a method for preparing chiral compounds, more particulary to method for preparing chiral compound by means of asymmetric ring opening reactions that the chiral salen catalyst can be simply recovered and reused, comprising reacting epoxides with nucleophiles in the presence of a salt followed formula 1 or mixture with other solvents and chiral salen metallic catalysts.
  • reaction Scheme 1 Reaction Scheme 1
  • nucleophiles in this reaction include N 3 " , NH 3 , H 2 NR, HNR 2 , H 2 0, ROH, PhOH, RSH, H " or RCH 2 P I .
  • the present invention is concerned with the use of the salt represented by the following formula 1.
  • Z is -C(R 5 )-
  • R 1 and R 2 are independently Ci-Ci ⁇ alkyl group
  • R 3 , R 4 and R 5 are independently hydrogen or C ⁇ -C s alkyl group; or if X is carbon atom
  • Z is -C (R 5 ) -C (R 6 ) -
  • R 1 is Ci-Ci ⁇ alkyl group
  • R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen or C ⁇ -C ⁇ 8 alkyl group
  • n is an integer of 1-3
  • Y is an anion capable of forming salts and represents either a negatively charged halogen element, MX k ⁇ or R 7 0 ⁇ , wherein M is selected from the group consisting of IB, 2B, IIIA, IVA and VA elements in periodic table of elements (CAS version) and X is halogen atom, k is an integer of 2-6, R is selected from the group consisting of alkyl sulfonyl, haloaklyl sulfonyl, phosphoryl and alkylcarbonyl .
  • C ⁇ -C ⁇ 8 alkyl group refers to primary, secondary or tertiary alkyls of C 1 -C1 8 , exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, 2-methyl-butyl, 3-methyl- butyl, hexyl, heptyl or octyl .
  • the salt is an imidazolium salt represented by the following formula 2 :
  • R 1 , R 2 , Y and n are the same as defined above.
  • imidazolium salt examples include cations of l-ethyl-3-methyl-imidazolium, l-methyl-3-propyl- imidazolium, l-butyl-3-methyl-imidazolium, l-methyl-3-pentyl- imidazolium, l-hexyl-3-methyl-imidazolium and l-heptyl-3- methyl-imidazolium with anion such as hexafluoroantimonate (SbF 6 ) , hexafluorophosphate (PF 6 ) , tetrafluoroborate (BF ) , trifluoromethanesulfonate (OTf) , acetate (OAc) and the like.
  • anion such as hexafluoroantimonate (SbF 6 ) , hexafluorophosphate (PF 6 ) , tetrafluoroborate (BF ) , trifluoromethan
  • ionic liquids exist as liquid phases at 100 °C or lower are called ionic liquids.
  • such an ionic liquid may be used as a sole solvent or in combination with other organic solvents.
  • Applicable in the latter case are ordinary organic solvents exemplified by benzene, toluene, chlorobenzene, diethyl ether, tetrahydrofurane, dioxane, dichloromethane, chloroform, ethyl acetate or acetonitrile.
  • the salts of the formula 1 have advantages of being highly stable to air and moisture, friendly to the environment and superior in thermal stability and exhibiting high solvation ability with no volatility and flammability. Also, the salts are well suited to catalytic reactions by virtue of their lack of the ability to form a coordinate bond to metals [P. Waaserscheid, W. Keim, Angew. Chem. Int . Ed. 2000, 39, 3772; T. Welton, Chem . Rev. 1999, 99, 2071; K.R. Seddon, J. Chem . Tech . Biotechnol . 1997, 68, 351; Y. Chauvin, H. Olivier, CHEMTECH, 1995, 26] .
  • the salts are able to make polar or ionic catalysts such as chiral salen catalysts immobilized in the ionic liquid or solvents and allow the products to be easily separated from the catalysts .
  • polar or ionic catalysts such as chiral salen catalysts immobilized in the ionic liquid or solvents and allow the products to be easily separated from the catalysts .
  • any chiral salen catalyst may be used in the production of chiral compounds through asymmetric ring opening of epoxides.
  • Chiral salen catalysts used in the present invention may be classified into various groups according to chemical structure: 1.
  • a preferred class of the chiral salen catalysts useful in the present invention have the structure represented by the following formula 3 : (Formula 3)
  • R 1 , R 2 , R 3 and R 4 are substituent groups to provide chirality to the structure, independently hydrogen, alkyl, carboxyl, aryl, substituted or non-substituted aryl group, wherein the substituent of aryl group is selected from the group consisting of haloge, alky, alkoxy, cyano or nitro group,
  • R 1 , R 2 , R 3 and R 4 can be bonded each other to form a C-Cs ring;
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 are independently hydrogen, halogen, alkyl, silyl, silyoxy, alkenyl, alkynyl, hydroxy, alkoxy, amino, nitro, cyano, thiol, thioether, imino, amido, phosphoryl, carbonyl and sulfonyl group.
  • Y 1 and Y 2 are independently hydrogen or alkyl group.
  • M represents metal, selected from the group consisting of
  • a ⁇ represents an anion, preferably selected from the group consisting of Cl ⁇ , N 3 ⁇ , CH 3 000 " , BF 4 P PF 6 " and SbF 6 P
  • Another class of the chiral salen catalysts useful in the present invention have the structure represented by the following formula 4 :
  • R 1 and R 2 are in trans-positions to each other, hydrogen, alkyl, carboxyl, substituted or non-substituted aryl group, wherein the substitutent of aryl group is selected from the group consisting of halogen, alkyl, alkoxy, cyano and nitro group;
  • R is selected from the group consisting of alkyl, aryl, alkyl carbonyl (-C (0) R) , aryl carbonyl (-C (0) r) , alkyl carboxyl (-C(O) OR) , aryl carboxyl (-C (0) OAr) , alkyl sulfonyl(- S(0) 2 R) and aryl sulfonyl group (-S(0) 2 Ar); n is an integer of 1-3,
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , Y 1 , Y 2 , M and A " are each the same as defined in the formula 3.
  • chiral salen catalysts of the formula 4 are represented by the following formula 4a and 4b [R. G. Konsler, J. Karl, E. N. Jacobsen, J. Am . Chem . Soc. , 1998, 120, 10780; C. E. Song et al . , Chem . Commun . 2000, 615].
  • the chiral salen catalysts useful in the present invention have the structure represented by the following formula 5 [Jacobsen et al . , US 6,665,890 (1997) and Jacobsen et al . , US 5,929,232 (1999)]. (Formula 5)
  • Z 1 , Z 2 , Z 3 and Z 4 are independently hydrogen, alkyl, halogen, cyano or nitro group;
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , Y 1 , Y 2 , M and A " are each the same as defined in the formula 3.
  • X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are independently hydrogen, halogen, alkyl, silyl, silyloxy, alkenyl, alkynyl, hydroxyl, amino, nitro, thio, thioether, cyano, imino, a ido, phosphryl, carbonyl or sulfonyl group; or X 1 and X 2 , X 4 and X 5 can be bonded each other to form a benzene ring;
  • R 5 , R 6 , R 7 and R 8 are independently alkyl, aryl, substituted or non-substituted aryl group, wherein the subsituent of aryl group is selected from the group consisting of halogen, alkyl, alkoxy, cyano and nitro group; or R 5 and R 6 , R 7 and R 8 can be bonded each other to form naphthyl group or alkyl- or aryl-substituted naphthyl group; R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 , M and A " each are the same as defined in the formula 3.
  • R 1 represents hydrogen or methyl group
  • R 2 represents methyl or phenyl group, and preferably phenyl group
  • M represents metal, and preferably Cr or Co
  • a " represents an anion, and preferably selected from the group consisting of Cl ⁇ , N 3 ⁇ and OAcP
  • the asymmetric ring opening of epoxides by nucleophiles in the presence of the chiral salen catalysts may be carried out in ordinary asymmetric ring opening conditions except that the salt of the formula 1 is used as a sole solvent or in combination with other organic solvent [US 5,665,890 (1997) and Jacobsen et al . , US 5,929,232 (1999), Jacobsen et al . , WO 9628402 (1996) and Jacobsen et al . , WO 0009463 (1999; L. E. Martinez, J. L. Leighton, D. H. Carsten, E. N. Jacobsen, J. Am . Chem . Soc. 1995, 117, 5897; M.
  • Nucleophiles for use in the asymmetric ring opening of epoxides include neutral compounds such as alcohols, water, amines, mercaptan and the like; anions such as akoxides, thiolates, carbanions, azides, cyanides, thiocyanides, acetates, formates, chloroformates, bisulfides and the like; organometallic reagents and hydrides such as organocuprates, organozinc compounds, organolithium compounds, Grignard reagents, enolates, acetylides, and the like. IV. Recovery of Chiral Salen Catalyst
  • any organic solvent may be used in this solvent extraction if it dissolves target compounds, that is, chiral compounds, but does not mix with the salt of the formula 1.
  • the organic solvents useful in the present invention include pentane, hexane, heptane, benzene, toluene, diethyl ether and isopropanol.
  • stirring is preferably conducted following the addition of the organic solvent. After the stirring, the reaction mixture is divided into two phases. Because the salt of the formula 1 is high in density, it gathers in the lower portion of the reactor, while the upper portion, that is, the organic phase, contains the reaction product. After removal of the organic phase by an ordinary method, the product may be separated from the organic phase by filtration, such as column chromatography, distillation or recrystallization. Thereafter, the chiral salen catalyst can be recovered from the salt layer which remains in the lower portion.
  • products may be separated directly by distillation.
  • the catalyst can be reused without additional separation, that is, as it stands dissolved in or dispersed throughout the salt. With its catalytic activity and enantioselectivity unchanged, the recovered chiral salen catalyst is also effectively applied to the asymmetric ring opening of epoxides .
  • EXAMPLE 3 Preparation of chiral azido alcohol and recovery of chiral catalyst
  • chiral salen catalyst having formula 3a (Cr-Cl, 38 mg, 0.06 mmol) and cyclohexene oxide (0.20 ml, 2 mmol) were added, and stirred in nitrogen atmosphere.
  • chiral salen catalyst having formula 3a (Cr-Cl, 38 mg, 0.06 mmol) and cyclohexene oxide (0.20 ml, 2 mmol) were added, and stirred in nitrogen atmosphere.
  • To 0.28 ml (2.1 mmol) of trimethylsilyl azide was slowly added to the imidazolium solution. The reaction solution was stirred while maintaining its internal temperature at 20 °C for 18 hours in a nitrogen atmosphere.
  • EXAMPLE 5 Preparation of chiral azido alcohol and recovery of chiral catalyst
  • chiral salen catalyst having formula 3a (Cr-Cl, 38 mg, 0.06 mmol) and 3,4- epoxytetrahydrofuran (173.5 mg, 2 mmol) were added, and stirred in nitrogen atmosphere.
  • chiral salen catalyst having formula 3a (Cr-Cl, 38 mg, 0.06 mmol) and 3,4- epoxytetrahydrofuran (173.5 mg, 2 mmol) were added, and stirred in nitrogen atmosphere.
  • To 0.28 ml (2.1 mmol) of trimethylsilyl azide was slowly added to the imidazolium solution. The reaction solution was stirred while maintaining its internal temperature at 20 °C for 28 hours in nitrogen atmosphere.
  • EXAMPLE 6 Preparation of chiral azido alcohol and recovery of chiral catalyst Except that SbF 6 salt of 3-butyl-l-methyl imidazolium (1 ml) was used instead of PFg salt, the reaction was performed in the same manner as described in Example 1, to obtained azido alcohol with 45 % yield and 97 % ee optical purity. The catalyst used was recovered as fixed in the salt. Yields, optical purities and preparation conditions of the azido alcohol compounds prepared in Examples 1 to 6 were summarized in Table 1, below. (TABLE 1)
  • EXAMPLE 10 Preparation of chiral azido alcohol and recovery of chiral catalyst Except that a solvent mixture of dichloromethane (1 ml) and a PFs salt of 3-butyl-l-methyl imidazolium (0.5 ml) were used, the reaction was performed in the same manner as described in Example 7, to obtained azido alcohol with 28 % yield and 65 % ee optical purity. The catalyst was recovered as it remained fixed with the salt.
  • EXAMPLE 12 Preparation of chiral azido alcohol and recovery of chiral catalyst Except that a solvent mixture of dichloromethane (2 ml) and a PF 6 salt of 3-butyl-l-methyl imidazolium (0.5 ml) were used, the reaction was performed in the same manner as described in Example 7, to obtained azido alcohol with 33 % yield and 85 % ee optical purity. The catalyst was recovered as it remained fixed with the salt.
  • the lower layer containing the salt of the formula 1 was added with water (10 ml) and vigorously stirred, as shown in the following reaction scheme 3.
  • the aqueous phase was added with diethyl ether to extract 1-phenyl-l, 2- ethanediol.
  • the styrene oxide of the hexane layer was measured for optical purity by gas chromatography using a Chrompack Chiral-DEX CB column. Under an isothermal condition of 80 °C, there was separated each enantiomer (7.8 min (R) , 8.7 min (S) ) .
  • the 1-phenyl-l, 2- ethanediol of the diethyl ether layer was subjected to gas chromatography using a Chrompack Chiral-DEX CB column. Under a thermal condition of maintenance at an initiation temperature of 120 °C for 20 min, temperature elevation at a rate of 1 °C/min, and maintenance at a final temperature of 140 °C for 5 min, its enantiomers were separated (28 min (S) , 29.3 min (R) ) .
  • the fractions were deprived of solvents in vacuo and loaded onto a column by use of a 1 % triethylamine buffer, followed by eluting with a solvent mixture of 1:6 acetic acid ethyl ester : hexane to produce pure styrene oxide 252.3 mg (42 % yield, 96 % ee) and eluting with a solvent mixture of 1:1 acetic acid ethylester : hexane to produce pure
  • the epichlorohydrin was measured for optical purity by gas chromatography using a Chiral-DEX ⁇ -TA column. In an isothermal condition of 40 °C, there was separated each enantiomer (16.0 min (S) , 20.6 min (R) ) .
  • a PF 6 salt of 3- butyl-1-methylimidazolium represented by the formula 1 (1.5 ml) and then styrene oxide (0.57 ml, 5 mmol) were added, and stirred together. Following the addition of water (0.063 ml, 3.5 mmol), stirring was conducted at room temperature for 44 hours. Subsequently, hexane (10 ml) was also added before the reaction was vigorously stirred for 30 min. After the upper layer (hexane layer) was removed, the lower layer containing the salt of the formula 1 was added with water (10 ml) and vigorously stirred.
  • the catalyst of the formula 3a can ensure a high production yield of 70 % or higher even when it is repeatedly used for the production of highly optically pure azido alcohols if its catalysis is conducted in a salt solvent of the formula 1.
  • EXPERIMENTAL EXAMPLE 2 Reuse of chiral catalyst
  • a chiral salen catalyst 38 mg, 0.06 mmol represented by the formula 3a in which M-A was Cr-Cl and a cyclopentene oxide (0.175 ml, 2 mmol) were added, along with a PF 6 salt (1 ml) and a trifluorosulfonate (CF 3 S0p, hereinafter referred to as "OTf") (0.5 ml) of 3-butyl-l- methylimidazolium, both represented by the formula 1, and stirred together under a nitrogen atmosphere. Following the slow addition of trimethylsilyl azide (0.28 ml, 2.1 mmol),
  • EXAMPLE 17 Preparation of chiral epoxide and chiral diol and recovery of chiral catalyst
  • (R, R) - (-) -N,N' -bis (3, 5-di-tert- butylsalicylidene) -1, 2-cyclohexanediamino cobalt (II) (30.2 mg, 0.05 mmol) was dissolved in dichloromethane (1.5 ml) and reacted with ferrocenium hexafluorophosphate (16.5 mg, 0.05 mmol) at room temperature for 2 hours with stirring to produce a catalyst represented by the formula 3a in which M-A was Co- PF 6 .
  • a catalyst (18.7 mg, 0.025 mmol) represented by the formula 3a in which M-A was Co-PF 6 was dissolved in a mixture of tetrahydrofuran (1.5 ml) and a PF 6 salt of 3-butyl-l-methylimidazolium (0.5 ml) represented by the formula 1 and reacted with epichlorohydrin (0.78 ml, 10 mmol) and water (0.126 ml, 7 mmol) at 20 °C for 24 hours with stirring. From the reaction mixture was extracted (S)- epichlorohydrin by fractional distillation under reduced pressure.
  • salts represented by the formula 1 or solvent systems containing the salts allow chiral salen catalysts to perform its catalytic activity with high enantioselectivity and efficiency in the asymmetric ring opening of epoxides, as well as ensuring the easy recovery of the catalysts without deteriorating the activity and enantioselectivity thereof nor changing their structures.
  • the method for preparing chiral compounds according to the present invention is very useful industrially.

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Abstract

L'invention concerne un procédé de préparation de composés chiraux par des réactions d'ouverture de cycle asymétrique d'époxydes, plus précisément, un procédé de préparation de composés chiraux au moyen de réactions d'ouverture de cycle asymétrique d'époxydes avec des nucléophiles en présence de liquides ioniques comme solvants et catalyseurs de métal-salen. Un tel procédé permet de faciliter la récupération et réutilisation d'un catalyseur onéreux dans lequel celui-ci conserve son activité et énantiosélectivité, de manière que des composés chiraux puissent être préparés de façon économique.
PCT/KR2001/000597 2000-08-05 2001-04-10 Procede de preparation de composes chiraux par des reactions d'ouverture de cycle asymetrique d'epoxydes WO2002012171A1 (fr)

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WO2008153280A1 (fr) * 2007-06-13 2008-12-18 Chirochem Co., Ltd. Nouveaux catalyseurs salen chiraux et procédé de préparation de composés chiraux à partir d'époxydes racémiques au moyen de ces catalyseurs
US7544749B2 (en) * 2003-02-07 2009-06-09 Basell Polyolefine Gmbh Polymerization catalysts, organic transition metal compounds, process for preparing polyolefins and polyolefins
CN112250871A (zh) * 2020-10-26 2021-01-22 上海麦豪新材料科技有限公司 一种炔基聚醚改性有机硅表面活性剂的制备方法

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2378701A (en) * 2001-07-04 2003-02-19 Shell Int Research Process for the preparation of alkylene glycols
EP1534699A4 (fr) * 2002-08-27 2007-01-10 Rhodia Pharma Solutions Inc Procede de resolution cinetique
US7544749B2 (en) * 2003-02-07 2009-06-09 Basell Polyolefine Gmbh Polymerization catalysts, organic transition metal compounds, process for preparing polyolefins and polyolefins
WO2008153280A1 (fr) * 2007-06-13 2008-12-18 Chirochem Co., Ltd. Nouveaux catalyseurs salen chiraux et procédé de préparation de composés chiraux à partir d'époxydes racémiques au moyen de ces catalyseurs
CN112250871A (zh) * 2020-10-26 2021-01-22 上海麦豪新材料科技有限公司 一种炔基聚醚改性有机硅表面活性剂的制备方法

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