JP2000334307A - Catalyst for asymmetric epoxidation of enones and method for producing optically active epoxide using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an asymmetric epoxidation catalyst for enones which gives high reactivity, high yield and high optical purity. SOLUTION: In the asymmetric epoxidation reaction of enones, ytterbium triisopropoxide (A) and
(R) -binaphthol (B), lutidine-N-oxide, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphortriamide, triphenylphosphine oxide, tri (2-methylphenyl) phosphine oxide And a catalyst containing one or more compounds (C) selected from the group consisting of and tri (4-methylphenyl) phosphine oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

 [Detailed description of the invention]

[0002]

[0001] The present invention relates to a catalyst composition for asymmetric organic synthesis. The catalyst composition of the present invention is useful for various organic asymmetric synthesis reactions. For example, in the asymmetric epoxidation reaction of enones, it shows high reactivity and gives a reaction product with high optical purity.

[0003]

BACKGROUND OF THE INVENTION The catalyst composition for asymmetric organic synthesis of the present invention is not known and is a novel catalyst. As a conventional catalyst for organic asymmetric synthesis, for asymmetric epoxidation reaction, lanthanum isopropoxide, the following general formula (6)

[0004]

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[0005] A catalyst solution comprising a binaphthol derivative, molecular sieve 4A, and tetrahydrofuran represented by (R ₁₄ represents hydrogen or a hydroxymethyl group, and * represents an optically active carbon) is known (Japanese Patent Application Laid-Open No. 10-1998).
120668).

[0006]

However, in the method described in Japanese Patent Application Laid-Open No. H10-120668, for example,
When tert-butyl hydroperoxide (hereinafter abbreviated as TBHP) is used as the oxidizing agent, the reaction at room temperature for 0.5 hour has a yield of 86%, an optical purity of 73% ee, and a low level of the target optically active epoxide. It can be obtained only in yield and low optical purity. Therefore, to get satisfactory results,
It is necessary to use cumene hydroperoxide (hereinafter abbreviated as CMHP) which is a special oxidizing agent. For example, the yield is 78 to 93% and the optical purity is 83 to 94% in a reaction of 6 hours or more.
ee (J. Am. Chem. Soc.
Vol. 119, No. 9, 1997, p2329-2
330).

[0007]

The present inventors have conducted intensive studies on the development of a catalyst having high reactivity and high optical purity, and as a result, have found the catalyst composition of the present invention and have completed the present invention. Was.

That is, the present invention provides (A) ytterbium ion, (B) the following general formula (1)

[0009]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; Linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkyloxyalkyl group having 2 to 10 carbon atoms, a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms An alkyloxyalkoxy group, a linear, branched or cyclic alkylamino group having 1 to 10 carbon atoms, an aromatic group having 5 to 14 carbon atoms, and a carbon number substituted with an alkyl group having 1 to 5 carbon atoms 5-
And 14 aromatic groups or halogen elements. The mark * indicates optically active carbon. ) Binaphthols,
And (C) the following general formula (2)

[0011]

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[Wherein R ₅ , R ₆ and R ₇ are each independently
A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aromatic group having 5 to 14 carbon atoms, an aromatic group having 5 to 14 carbon atoms substituted with an alkyl group having 1 to 5 carbon atoms, Or -N
R ₈ R ₉ (where R ₈ and R ₉ each independently represent 1 to ₉ carbon atoms)
10 straight-chain, branched or cyclic alkyl groups, C 5-14 aromatic groups, C 1-5 straight-chain, branched or substituted with C 5-14 aromatic groups It represents a cyclic alkyl group or an aromatic group substituted with an aromatic group having 5 to 14 carbon atoms, and R ₈ and R ₉ may be bonded to each other to represent an alkylene group having 2 to 6 carbon atoms. ). And a compound represented by the following general formula (3)

[0013]

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Wherein A represents carbon and nitrogen. When A is carbon, R ₁₀ and R ₁₁ are each independently an amino group disubstituted with a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms (wherein R ₁₀ and R 11 ₁₁ are connected to each other and A
Together with a nitrogen-containing ring), or 5-1 carbon atoms
4 represents an amino group disubstituted with an aromatic group, and the bond to oxygen represents a double bond. When A is nitrogen, R ₁₀ and R ₁₁ are bonded to each other to form a nitrogen-containing aromatic ring together with A, and the bond to oxygen is a single bond. ] A catalyst composition for organic asymmetric synthesis, characterized by containing one or more compounds selected from the group consisting of compounds represented by the following general formula (4) in the presence of this catalyst composition: )

[0015]

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(Wherein R ₁₂ and R ₁₃ each independently represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms;
C5-C14 aromatic group, C5-C14 aromatic group substituted with C1-C5 alkyl group, C1-C5-alkoxy group substituted with C1-C5 alkoxy group Carbon number 5-1
An aromatic group having 4 to 5 carbon atoms, an aromatic group having 5 to 14 carbon atoms substituted with 1 to 5 halogen atoms, and a linear or branched C 1 to 6 aromatic group substituted with an aromatic group having 5 to 14 carbon atoms. Or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms substituted with a cyclic alkyl group or a halogenated aromatic group having 5 to 14 carbon atoms. ) And an oxidizing agent, wherein R ₁₂ , R _12
13 has the same definition as in the general formula (4), and * indicates an optically active carbon. ) Is a method for producing an optically active epoxide.

The present invention will be described in detail below.

The catalyst composition of the present invention comprises (A) ytterbium ion, (B) binaphthols of the above general formula (1), (C) a compound of the above general formula (2) and a compound of the above general formula (2) 3) containing one or more compounds selected from the compounds represented by 3), exhibiting higher reactivity and higher optical purity than conventional organic asymmetric synthesis catalysts. give. Incidentally, the organic synthesis catalyst of the present invention includes not only an aggregate of ionic bond-coordination bond but also an aggregate of covalent bond-coordination bond. , "Ion".

In the catalyst composition of the present invention, the ytterbium ion used as the component (A) is not particularly limited, but specifically, ytterbium methoxide, ytterbium ethoxide, ytterbium n-propoxide, Ytterbium isopropoxide, ytterbium alkoxides prepared from aliphatic alcohols such as ytterbium n-butoxide, ytterbium trifluoromethanesulfonate, ytterbium sulfonates such as ytterbium pentafluoroethane sulfonate, ytterbium chloride,
It can be obtained from ytterbium halides such as ytterbium bromide and ytterbium iodide.

In the catalyst composition of the present invention, the binaphthol represented by the above general formula (1) used as the component (B) is not particularly limited, but specifically, the (R) form As (R) -binaphthol,
(R) -3,3'-dimethoxybinaphthol, (R)-
3,3′-methoxyethoxyethoxybinaphthol,
(R) -6,6'-diphenylbinaphthol, (R)-
6,6′-dibromobinaphthol, (R) -6,6′-
Dinaphthyl binaphthol, (R) -6,6′-dimethoxybinaphthol and the like. In addition, (S) -forms that are stereoscopically mirrored with these include (S) -binaphthol, (S) -3,3′-dimethoxybinaphthol,
(S) -3,3′-methoxyethoxyethoxybinaphthol, (S) -6,6′-diphenylbinaphthol,
(S) -6,6'-dibromobinaphthol, (S)-
6,6′-dinaphthylbinaphthol, (S) -6,6 ′
-Dimethoxybinaphthol and the like, which are properly used depending on the purpose.

In the catalyst composition of the present invention, one or two or more compounds selected from the compound represented by the general formula (2) and the compound represented by the general formula (3) used as the component (C) are used. The compound is not particularly limited.

For example, as the compound represented by the general formula (2), specifically, triphenylphosphine oxide, tri (2-methylphenyl) phosphine oxide, tri (3-methylphenyl) phosphine oxide , Tri (4-methylphenyl) phosphine oxide, methyldiphenylphosphine oxide,
Methoxymethyl (diphenyl) phosphine oxide, tri-n-butylphosphine oxide, tri-n
-Octylphosphine oxide, tri (cyclohexyl) phosphine oxide and the like. Also,
Phosphoric triamides such as hexamethylphosphoric triamide and tripiperidinophosphine oxide. As the compound represented by the general formula (3), specifically, 1,3-dimethyl-2-imidazolidinone,
2,6-lutidine-N-oxide and the like. The compound represented by the general formula (2) and the general formula (3)
Among the one or more compounds selected from the group consisting of the compounds represented by the formula (I), the compound represented by the general formula (2) is preferable, and the triphenylphosphine oxide, tri (p- Methylphenyl)
Phosphine oxide, hexamethylphosphoric triamide and tripiperidinophosphine oxide.

In the catalyst composition of the present invention, it is preferable to use a cationic or anionic species for charge neutralization. As the cationic or anionic species for charge neutralization, since the ytterbium ion has a trivalent valence, when the binaphthols are used in an amount of 1.5 mol times or more with respect to the ytterbium ion, the cationic species or the anionic species is used. When used in an amount of less than 1.5 molar times, an anionic species is used.

For example, the cation species is an alkali metal ion or an alkaline earth metal ion, and is not particularly limited. Specifically, lithium ions, sodium ions, potassium ions, rubidium ions,
Examples include beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion and the like. The anionic species is not particularly limited, but may be, for example, a linear, branched or cyclic alkyloxy ion having 1 to 20 carbon atoms, a linear, branched or cyclic alkylthio ion having 1 to 20 carbon atoms. An ion, an alkyloxy ion having 1 to 8 carbon atoms substituted with an aromatic group having 5 to 12 carbon atoms, an alkylthio ion having 1 to 8 carbon atoms substituted with an aromatic group having 5 to 12 carbon atoms, a halogen ion, Examples include ions selected from the group consisting of perhalate ions, tetrafluoroborane ions, and fluorinated alkyl sulfonate ions, and specifically, methoxy ions, ethoxy ions, n-propoxy ions,
i-propoxy ion, n-butoxy ion, i-butoxy ion, tert-butoxy ion, n-pentoxy ion, i-pentoxy ion, cyclopentoxy ion, n-hexyloxy ion, i-hexyloxy ion , Cyclohexyloxy ion, n-heptyloxy ion, n-octyloxy ion, 2-cyclohexylethoxy ion, n-nonyloxy ion, n-
Undecyloxy ion, n-pentadecyloxy ion, methylthio ion, ethylthio ion, n-propylthioion, i-propylthioion, n-butylthioion, i-butylthioion, tert-butylthioion, n -Pentylthioion, i-pentylthioion, cyclopentylthioion, n-hexylthioion, i-hexylthioion, cyclohexylthioion, n-heptylthioion, n-octylthioion, 2- Cyclohexylethylthio ion, n-nonylthio ion, n-undecylthio ion, n-pentadecylthio ion, benzyloxy ion, diphenylmethyloxy ion, benzylthio ion, diphenylmethylthio ion, fluorine ion, chloride ion, Bromine ion, iodine ion , Perchlorate ion, perbromic acid ion, perbromic acid ion, tetrafluoro borane ion, trifluoromethanesulfonate ion, pentafluoroethane sulfonic acid ion, and the like. Of these, preferred are an alkyl oxide ion and an aromatic alkyl oxide ion, and more preferred are a methoxy ion, an ethoxy ion, an n-propoxy ion, and i.
-Propoxy ion, n-butoxy ion, i-butoxy ion, tert-butoxy ion, chloride ion, bromine ion, iodine ion, perchlorate ion, perbromate ion, perbromate ion, tetrafluoroborane ion,
Trifluoromethanesulfonate ion and pentafluoroethanesulfonate ion.

In the catalyst composition of the present invention, the above (A)
The composition ratio of each of the components (C) to (C) is not particularly limited, but usually, (A) 1 mol of ytterbium ion and (B) 1 to 3 mol of binaphthol represented by the above general formula (1). And (C) 1 to 10 moles of one or more compounds selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3).

The method for preparing the catalyst composition of the present invention is not particularly limited. For example, (A) ytterbium ion, which is a component of the catalyst composition of the present invention, and (B) a compound represented by the above general formula (1) Reacting one or more compounds selected from the group consisting of binaphthols represented by (C) a compound represented by the above general formula (2) and a compound represented by the above general formula (3) in a solvent. Can be prepared.

As the solvent applicable to the method for preparing the catalyst composition of the present invention, any solvent can be used as long as it is inert to the catalyst and the reaction to be applied. From the viewpoint of the reaction results of the asymmetric synthesis reaction, ether solvents such as dimethyl ether, diisopropyl ether, 1,2-dimethoxyethane, and tetrahydrofuran (hereinafter abbreviated as THF) are preferable.

After preparation, the catalyst composition of the present invention can be used in various reactions as a catalyst solution without isolation and purification.

The catalyst composition of the present invention can be applied to various organic asymmetric synthesis reactions. Available reactions differ depending on the type of ytterbium ion and the composition ratio of the components. Specifically, asymmetric aldol condensation reaction, asymmetric epoxidation reaction, asymmetric Diels-Alder cyclization reaction, asymmetric hetero-diels reaction, Alder cyclization, asymmetric reduction, asymmetric protonation, asymmetric nitroaldol, asymmetric Michael addition, asymmetric hydrophosphonylation, asymmetric Michael-aldol, and other asymmetric induction reactions And provides high reactivity for each of these reactions and gives the products high optical purity.

The optical absolute configuration developed by reacting with the catalyst composition of the present invention generally depends on the optical absolute configuration of binaphthol constituting the catalyst. For example, when (R) -binaphthol is used, a substrate whose optical absolute configuration of the asymmetric carbon of the product is (R) is (S)-
When binaphthol is used, the optically absolute configuration of the asymmetric carbon of the product is in the (S) configuration. In addition, regarding the optical absolute configuration of the asymmetric carbon of the product, when (R) -binaphthol is used, the optical absolute configuration of the asymmetric carbon of the product does not necessarily become the (R) form, but the type of the substrate, etc. The absolute optical configuration of the product differs depending on the product.

When the organic synthesis catalyst of the present invention is applied to various organic asymmetric synthesis reactions, the amount of the catalyst used is not particularly limited, but the number of moles of ytterbium ions relative to the substrate used in the reaction is not limited. 0.01 to 5 on the basis of
0 mol%, preferably in the range of 0.1 to 25 mol%.

Hereinafter, the asymmetric epoxidation reaction of enones will be specifically described as an application example of the catalyst composition of the present invention. However, it goes without saying that the catalyst composition of the present invention is not limited to this application example. Absent.

When the organic synthesis catalyst of the present invention is applied to an asymmetric epoxidation reaction of enones, it is preferable to prepare a catalyst solution in advance and use it for the reaction.

The catalyst solution of the present invention comprises (A) ytterbium ion, (B) which is a component of the catalyst catalyst composition of the present invention.
Binaphthols represented by the general formula (1), and (C) one or more kinds selected from the group consisting of the compounds represented by the general formula (2) and the compounds represented by the general formula (3) The compound can be prepared by reacting the compound in an ether solvent. Examples of ether solvents include dimethyl ether, diisopropyl ether,
1,2-dimethoxyethane, THF and the like are preferably used.

In the catalyst solution of the present invention, the ytterbium ion of the component (A) applicable to the asymmetric epoxidation reaction of enones is not particularly limited, and any ytterbium ion can be applied. Ytterbium ions, for example,
Ytterbium methoxide, ytterbium ethoxide, ytterbium n-propoxide, ytterbium isopropoxide, ytterbium alkoxides prepared from aliphatic alcohols such as ytterbium n-butoxide, ytterbium trifluoromethanesulfonate, ytterbium pentafluoroethanesulfonate And the like, and ytterbium halides such as ytterbium chloride, ytterbium chloride, ytterbium bromide and ytterbium iodide.

In the catalyst solution of the present invention, (B) the amount of the binaphthol represented by the general formula (1) is usually 1 to 3 mol per 1 mol of the ytterbium ion as described above. However, theoretically, it is particularly preferable to use an equimolar amount of (A) ytterbium ion and (B) binaphthols in terms of yield and optical purity. In practice, it is sufficient that (A) ytterbium ions are not present in excess with respect to (B) binaphthols, and that (A) ytterbium ions are 0.8 to 1.0 moles per mole of (A) binaphthols. It is particularly preferred to carry out the asymmetric epoxidation reaction of enones in the range of in this case,
Since (B) 1.5 mol or less of binaphthols is present per 1 mol of (A) ytterbium ions, about 1 mol of anionic species of the ytterbium compound used for obtaining ytterbium ions is present for charge neutralization. . The anion species can be converted to another anion species by further reacting.

In the catalyst solution of the present invention, the component (C) which is applicable to the asymmetric epoxidation reaction of enones comprises a compound represented by the general formula (2) and a compound represented by the general formula (3). As the one or more compounds selected from the group, any applicable and not particularly limited, but preferably a compound represented by the general formula (2), the yield and the optical purity of which From the viewpoint, triphenylphosphine oxide, tri (4-methylphenyl) phosphine oxide, hexamethylphosphortriamide, and tripiperidinophosphine oxide are more preferable.

Use of one or more compounds selected from the group consisting of the compound represented by the general formula (2) and the compound represented by the general formula (3) as the component (C) in the catalyst solution of the present invention. As described above, the amount is usually 1 to 10 moles per 1 mole of (A) ytterbium ion, but in order to form a more stable catalyst, the amount is 1.1 to 1 mole per (A) ytterbium ion. It is preferably used in a molar amount of at least 1.5 times, more preferably 1.5 times or more.

As a solvent applicable to the method of the present invention, any solvent can be used as long as it is an inert solvent for the catalyst and the epoxidation reaction. , Diisopropyl ether, 1,2-dimethoxyethane, and tetrahydrofuran (hereinafter abbreviated as THF) are preferable, and among them, THF gives the highest result.

The amount of the solvent used is in the range of 2 to 200 times, more preferably 5 to 100 times the weight of the enone used in the reaction in terms of weight.

As the enone applicable to the method of the present invention, any compound can be applied as long as it is a compound represented by the above general formula (4), and specifically, methyl vinyl ketone, trans-3- Penten-2-one, tra
ns-3-hexen-2-one, trans-3-hepten-2-one, trans-3-octen-2-one, trans-3-nonen-2-one, ethyl vinyl ketone, trans-4-hexen- 3-on, tra
ns-4-hepten-3-one, trans-4-octen-3-one, trans-4-nonen-3-one,
Isopropyl vinyl ketone, trans-2-methyl-
4-hexen-3-one, trans-2-methyl-4
-Hepten-3-one, trans-2-methyl-4-
Octen-3-one, trans-2-methyl-4-nonen-3-one, trans-1,3-diphenyl-2
-Propylene-1-one (chalcone), trans-
2-methyl-5-phenyl-4-penten-3-one,
4-methyl-1-phenyl-3-penten-2-one,
4-phenyl-3-butylen-2-one, 6-phenyl-3-hexen-2-one, 5-phenyl-3-hexen-2-one and the like.

In the method of the present invention, TBHP is usually used as an oxidizing agent. As TBHP, a commercially available solution such as decane may be used as it is, or a toluene solution is extracted from a 70% or 90% aqueous solution, dried with magnesium sulfate, and the like.
It may be used in the present invention. Also, there is no problem even if other oxidizing agents such as cumene peroxide are used without being limited to TBHP.

The amount of the oxidizing agent used is theoretically equivalent to the amount of the enone used in the reaction, but it is preferably at least 1.1 times the amount of the oxidizing agent in order to complete the reaction.

The reaction temperature in the method of the present invention differs depending on the substrate of the enone, but is usually from -50 ° C to 100 ° C.
The reaction is usually completed within 24 hours, and particularly when triphenylphosphine oxide is used, the reaction is completed within 2 hours in most cases.

For the purpose of dehydrating the system during catalyst preparation and reaction, and accelerating the catalyst formation reaction and epoxidation reaction, zeolite is preferably used in an amount of about 1 wt. As the type of zeolite, various zeolites such as A type zeolite represented by molecular sieves 3A, 4A and 5A, molecular sieves 13X, Y type and L type can be applied, but the molecular sieve 4A
Is particularly preferred.

After the completion of the reaction, the desired α, β-epoxy ketone is obtained in high yield and high optical purity by purifying by post-treatment, column chromatography or the like.

When an asymmetric epoxidation reaction of an enone is carried out using the catalyst solution of the present invention, generally, when (R) -binaphthol is used, the 2-position (α-position) of the resulting epoxide of the enone is obtained. And the optical absolute configuration of the third position (β position) is (2S,
3R), and if (S) -binaphthol is used,
(2R, 3S).

[0048]

The catalyst composition of the present invention is useful for various organic asymmetric synthesis reactions. In addition, the catalyst composition of the present invention provides an asymmetric epoxidation reaction of enones with high reactivity, high yield, and high optical purity, so that the method of the present invention is a method for producing various medical and agricultural chemical intermediates. Is extremely useful.

[0049]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the examples. In addition, the test of the optical purity of the product was implemented as follows.

That is, the reaction was carried out by high performance liquid chromatography equipped with a chiral column OB-H or AD of Daicel Corporation, elution solvent: Hexane / i-PrOH = 2
/ 1 to 100/1 (vol / vol), flow rate 1 ml / m
Measured in.

Trans-2,3-epoxy-1,3-
In the case of diphenylpropan-1-one, the chiral column O
Using BH, elution solvent: Hexane / i-PrOH
= 2/1, flow rate 1 ml / min, retention time 2
At 4 minutes, the peak of each enantiomer of (2S, 3R form) and at 32 minutes, the peak of each enantiomer of (2R, 3S form) appeared.

Example 1 Molecular sieves 4A was placed in a 10 ml eggplant-shaped flask.
(506 mg), and the mixture was heated under a reduced pressure with a vacuum pump for 30 minutes with a heat gun and dried. After cooling to room temperature, triphenylphosphine oxide (21.2 mg,
0.0758 mmol), (R) -binaphthol (7.
2 mg, 0.0251 mmol) and a magnetic stirrer chip, and the reaction system was replaced with argon gas. Then, THF (1 ml) was added and dissolved by stirring for 5 minutes, and then ytterbium isopropoxide (Y
b (O-iPr) ₃ , 8.86 mg, 0.0253 mm
ol) in THF (1.52 ml), and stirred for 1 hour to prepare a catalyst solution.

A decane solution of TBHP (5 M, 0.15 ml, 0.76 mmol) was added to the obtained catalyst solution,
After stirring for 0 minutes, chalcone (105.4 mg, 0.50 mg
(6 mmol) in THF (1 ml) was added to carry out a reaction. The progress of the reaction was confirmed by silica gel thin layer chromatography to have ended after 1.5 hours.

After completion of the reaction, 500 mg of silica gel and 3 ml of methanol were added, and the mixture was stirred for 15 minutes. Then, the residue was obtained by filtration and concentration, and a silica gel column (Hexa
ne / AcOEt = 30/1) to give trans- (2S, 3R) -epoxy-1,3-diphenylpropan-1-one in a yield of 98% and an optical purity of 8
6% ee).

Example 2 The same operation as in Example 1 was carried out except that TBHP was changed to CMHP, and trans- (3S, 4R) -epoxy was reacted for 4.5 hours. -4-
Phenylbutan-2-one was obtained at a yield of 88% and an optical purity of 83.
% Ee.

Comparative Example 1 Using the same reaction apparatus as in Example 1, except that ytterbium isopropoxide was changed to lanthanum isopropoxide and triphenylphosphine oxide was not added, the same reagent as in Example 1 was used. The operation was performed, and the reaction was carried out for 3 hours. Trans- (2S, 3R) -epoxy-1,3
-Diphenylpropan-1-one was obtained with a yield of 86% and an optical purity of 73% ee.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300 C07M 7:00 F term (Reference) 4C048 AA01 BB15 CC01 UU02 UU03 XX02 4G069 AA06 AA08 AA09 BA27A BA27B BA36A BC44A BC44B BE06A BE06B BE06C BE16C BE19A BE19C BE25C BE29A BE29B BE29C BE37A BE37B BE37C BE38A BE38C CB01 CB07 CB57 CB73 DA02 FA01 AC08 FC02 FC02 FC02

Claims (8)

[Claims] (A) ytterbium ion; (B) the following general formula (1): (Wherein, R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen, a linear or branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms) , Branched or cyclic alkoxy group, C2-C10 linear, branched or cyclic alkyloxyalkyl group, C2-C10 linear, branched or cyclic alkyloxy Alkoxy group, linear, branched or cyclic alkylamino group having 1 to 10 carbon atoms, aromatic group having 5 to 14 carbon atoms, 1 carbon atom
Represents an aromatic group having 5 to 14 carbon atoms or a halogen element substituted with an alkyl group having 5 to 5 carbon atoms. The mark * indicates optically active carbon. ), And (C)
The following general formula (2) [Wherein, R ₅ , R ₆ , and R ₇ each independently represent a carbon atom of 1 to 1;
0 linear, branched or cyclic alkyl group, 5 carbon atoms
To 14 aromatic groups, C 5 to C 14 aromatic groups substituted with C 1 to C 5 alkyl groups, or —NR ₈ R ₉ (where R ₈ and R ₉ are each independently C1-C10 linear, branched or cyclic alkyl group, C5-C14 aromatic group, C1-C5 linear group substituted with C5-C14 aromatic group Represents a branched or cyclic alkyl group, an aromatic group substituted with an aromatic group having 5 to 14 carbon atoms,
R ₈ and R ₉ may combine to represent an alkylene group having 2 to 6 carbon atoms. ). And a compound represented by the following general formula (3): [Wherein, A represents carbon and nitrogen. When A is carbon,
R ₁₀ and R ₁₁ are each independently a straight chain having 1 to 10 carbon atoms;
An amino group disubstituted with a branched or cyclic alkyl group (in this case, R ₁₀ and R ₁₁ may be bonded to each other to form a nitrogen-containing ring together with A), or an aromatic group having 5 to 14 carbon atoms Represents an amino group disubstituted by a group, and the bond to oxygen represents a double bond. When A is nitrogen, R ₁₀ and R ₁₁ are bonded to each other to form a nitrogen-containing aromatic ring together with A, and the bond to oxygen is a single bond. ] The catalyst composition for organic asymmetric synthesis characterized by containing one or more compounds selected from the group consisting of the compounds represented by the formula: 2. (A) 1 mol of ytterbium ion ions, (B) 1 to 3 mol of a binaphthol represented by the general formula (1), and (C) a compound represented by the general formula (2) and The catalyst composition according to claim 1, wherein the catalyst composition contains 1 to 10 mol of one or more compounds selected from the group consisting of compounds represented by the general formula (3). (B) The binaphthols represented by the general formula (1) are (R) -binaphthol, (R) -3,3′-
Dimethoxybinaphthol, (R) -3,3'-methoxyethoxybinaphthol, (R) -6,6'-diphenylbinaphthol, (R) -6,6'-dibromobinaphthol, (R) -6,6'-di Naphthyl binaphthol,
(R) -6,6'-dimethoxybinaphthol, (S)-
Binaphthol, (S) -3,3'-dimethoxybinaphthol, (S) -3,3'-methoxyethoxybinaphthol, (S) -6,6'-diphenylbinaphthol,
(S) -6,6'-dibromobinaphthol, (S)-
6,6′-dinaphthylbinaphthol and (S) -6
3. The catalyst composition according to claim 1, wherein the catalyst composition is a compound selected from the group consisting of 6′-dimethoxybinaphthol. 4. 4. The compound represented by the general formula (2) is selected from the group consisting of triphenylphosphine oxide, tri (p-methylphenyl) phosphine oxide, hexamethylphosphoric triamide and tripiperidinophosphine oxide. The catalyst composition according to any one of claims 1 to 3, which is a selected compound. 5. In the presence of the catalyst composition according to any one of claims 1 to 4, the following general formula (4): (Wherein R ₁₂ and R ₁₃ are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
An aromatic group having 4 to 5 carbon atoms, an aromatic group having 5 to 14 carbon atoms substituted with 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and 5 to 5 carbon atoms substituted with 1 to 5 alkoxy groups having 1 to 5 carbon atoms. 14 aromatic groups, an aromatic group having 5 to 14 carbon atoms substituted by 1 to 5 halogen atoms, a linear or branched C 1 to 6 aromatic group substituted by an aromatic group having 5 to 14 carbon atoms Or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms substituted with a cyclic alkyl group or a halogenated aromatic group having 5 to 14 carbon atoms. Wherein an enone represented by the formula) is reacted with an oxidizing agent. (In the formula, R ₁₂ and R ₁₃ have the same definition as in the general formula (4), and * indicates an optically active carbon.) 6. A catalyst solution for organic asymmetric synthesis, comprising the catalyst composition according to claim 1 and an ether-based solvent. 7. A catalyst solution for organic asymmetric synthesis, comprising the catalyst composition according to any one of claims 1 to 4, a zeolite and an ether solvent. 8. In the presence of the catalyst according to any one of claims 1 to 4, the following general formula (4): (Wherein R ₁₂ and R ₁₃ are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
An aromatic group having 4 to 5 carbon atoms, an aromatic group having 5 to 14 carbon atoms substituted with 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and 5 to 5 carbon atoms substituted with 1 to 5 alkoxy groups having 1 to 5 carbon atoms. 14 aromatic groups, an aromatic group having 5 to 14 carbon atoms substituted by 1 to 5 halogen atoms, a linear or branched C 1 to 6 aromatic group substituted by an aromatic group having 5 to 14 carbon atoms Or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms substituted with a cyclic alkyl group or a halogenated aromatic group having 5 to 14 carbon atoms. ) And an oxidizing agent are reacted with the following general formula (5): (In the formula, R ₁₂ and R ₁₃ have the same definition as in the general formula (4), and * indicates an optically active carbon.)