JP3296919B2 - Method for producing optically active cyclic compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an optically active cyclic compound useful as a synthetic intermediate for a physiologically active compound such as iridoid or eicosanoid.

[0002]

2. Description of the Related Art Hitherto, as a method for synthesizing an optically active cyclic compound by reacting cyclopentadiene with an olefin, several methods using an optically active Lewis acid catalyst have been proposed. are [journal of the Chemical Society, Chemical Communication's (J. Chem. Soc., Chem . Commu
n.), p. 437 (1979); Helvetica Chimka Acta, Vol. 70, p. 436 (1987); Journal of the American Chemical Society (J. Am. Chem. Soc.), 110. Volume, 310 pages (1988
Year); Journal of the American Chemical Society (J. Am. Chem. Soc.), 111, 5340 (19
1989); Journal of the American Chemical
Society (J. Am. Chem. Soc.), 111, 5549 (1
989); Tetrahedro asymmetry
n Asym.), 2: 639 (1991); tetrahedron
Tetrahedron Asym., Vol. 2, p. 643 (1991); Synthesis, p. 1, (1991)
Year) etc.).

As a method using an optically active lanthanoid catalyst, a method using an optically active europium compound as a nuclear magnetic resonance shift reagent is also known, but the optical yield is not so high [tetrahedron] Letters (Tetrahedron Letters), 24, 3451 (1983)
reference〕.

Further, according to the conventional production method, a specific configuration of the optically active cyclic compound can be obtained, but an optically active cyclic compound having the opposite configuration cannot be obtained.

It is an object of the present invention to provide a method for producing an optically active cyclic compound having a configuration opposite to that of a product obtained by a conventional method for producing an optically active cyclic compound in a high yield.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, in the production of an optically active cyclic compound, the coexistence of 1,3-diketone enables 1,3-diketone. In the absence of the compound, it was found that the reaction proceeded in a high yield even with a less reactive catalyst, and that a product having a reversed stereochemistry was obtained in a high optical yield, leading to the completion of the present invention. Was.

That is, the present invention provides a compound of the formula (I)

[0008]

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(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxyl group, an aralkyloxy group, a protected hydroxyl group, a halogen atom, a cyano group, an alkoxycarbonyl group, an acyl group, an aralkyl group or an aryl group, which may have a substituent group, R ⁴ represents an electron withdrawing group. also, R ¹ and R ^2, R ³ and the olefin R ⁴ or R ² and R ^4, is represented by it.) also shows a group forming a ring together, the formula (II)

[0010]

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(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxyl group, an aralkyloxy group A protected hydroxyl group, a halogen atom, a cyano group, a disubstituted amino group, an aralkyl group or an aryl group, which may have a substituent, and R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁵ and R ⁷ , R
⁸ and R ¹⁰ , R ⁹ and R ¹⁰ , or R ⁶ and R ⁹ may together represent a ring-forming group. Wherein the diene represented by the formula (III) is reacted in the presence of an optically active Group IIIb metal catalyst and 1,3-diketone.

[0012]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are as defined above. )).

Each symbol used in the present specification is described below. The alkyl group in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ is a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. , Isobutyl group, t-
Examples thereof include a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a tetradecyl group, a heptadecyl group and an icosyl group, and are preferably an alkyl group having 1 to 10 carbon atoms.

The cycloalkyl group represented by R ^{1 to} R ³ and R ^{5 to} R ¹⁰ is a cycloalkyl group having 3 to 7 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group. And the like, and preferably a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The alkenyl group in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ is a linear or branched alkenyl group having one or more double bonds and having 2 to 20 carbon atoms. ,
Examples thereof include a 4-methyl-3-pentenyl group and a 4,8-dimethyl-3,7-nonadienyl group.

The alkoxyl group in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ is a linear or branched alkoxyl group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group,
Examples thereof include an allyloxy group, a t-butoxy group, and a hexyloxy group, and a methoxy group and a t-butoxy group are preferable.

The aralkyloxy group in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ includes, for example, a benzyloxy group.

Examples of the protected hydroxyl group in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ include an acyloxy group such as an acetoxy group, a propionyloxy group, a benzoyloxy group and a trifluoroacetyloxy group; a methoxycarbonyloxy group;
An alkoxycarbonyloxy group such as an ethoxycarbonyloxy group and a t-butoxycarbonyloxy group; an aralkyloxycarbonyloxy group such as a benzyloxycarbonyloxy group; a trimethylsilyloxy group, a triethylsilyloxy group, a t-butyldimethylsilyloxy group;
a tri-substituted silyloxy group such as a t-butyldiphenylsilyloxy group; an alkoxyalkoxy group such as a methoxymethoxy group and an ethoxyethoxy group; a tetrahydropyranyloxy group; and the like, preferably an acetoxy group, a benzoyloxy group, a trimethylsilyloxy group, It is a t-butyldimethylsilyloxy group.

Examples of the halogen atom in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the aralkyl group in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ include a benzyl group, a methoxybenzyl group, a chlorobenzyl group, a methylbenzyl group, a phenethyl group and a phenylpropyl group. It is.

The aryl group represented by R ^{1 to} R ³ and R ^{5 to} R ¹⁰ includes a phenyl group and a naphthyl group, and is preferably a phenyl group.

The alkoxycarbonyl group for R ^{1 to} R ³ is a straight-chain or branched-chain alkoxycarbonyl group having 2 to 6 carbon atoms, the alkoxy portion of which is the same as described above. Carbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, t-
Examples include a butoxycarbonyl group, and preferred are a methoxycarbonyl group, an ethoxycarbonyl group, and a t-butoxycarbonyl group.

The acyl group represented by R ^{1 to} R ³ is an alkanoyl group having 1 to 20 carbon atoms, an aroyl group or the like, and specific examples thereof include a formyl group, an acetyl group, a trifluoroacetyl group, a propionyl group and a benzoyl group. And the like, and preferably an acetyl group or a benzoyl group.

The disubstituted amino group in R ^{5 to} R ¹⁰ may have an alkyl group, an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group or the like as a substituent. May be used. Specifically, a dialkylamino group or a diaralkylamino group such as a dimethylamino group, a diethylamino group, a diisopropylamino group, or a dibenzylamino group; an alkylarylamino group or an aralkylarylamino group such as a methylphenylamino group or a benzylphenylamino group Cyclic amino group such as pyrrolidinyl group, piperidinyl group, piperazinyl group, N-methylpiperazinyl group, N-benzylpiperazinyl group, N-methylhomopiperazinyl group; methylformylamino group, methylacetylamino group Acylamino groups such as benzylformylamino group and phenylacetylamino group; alkoxycarbonylamino groups such as methylmethoxycarbonylamino group and phenylmethoxycarbonylamino group; and imide groups such as phthalimide group and succinimide group. It is.

The above-mentioned groups in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ may have a substituent as described in some of the specific examples, and the substituent may be an alkyl group. , A cycloalkyl group, an alkenyl group, an alkoxyl group, a protected hydroxyl group, a halogen atom, a disubstituted amino group, a cyano group, an aralkyl group or an aryl group (the same as described above).

Examples of the electron-withdrawing group for R ⁴ include an acyl group (as described above), a carboxyl group, an alkoxycarbonyl group (as described above), a substituted or unsubstituted carbamoyl group, a cyano group, a nitro group, an alkane sulfonyl group. Groups (the alkane portion is the same as the above-described alkyl group), and arene sulfonyl group (the arene portion is the same as the above-described aryl group). Examples of the substituted carbamoyl group include a (2-oxo-1,3-oxazolidin-3-yl) carbonyl group and a dimethylaminocarbonyl group, and preferably (2-oxo-1,3-oxazolidine-3-yl). Yl) a carbonyl group.

In R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , or R ⁹ and R ¹⁰ , the group forming a ring includes a tetramethylene group, a pentamethylene group, an oxatrimethylene group, Examples thereof include an ethylenedioxy group and the like, which together with an adjacent carbon form a 5- or 6-membered ring.

R ² and R ⁴ , R ⁵ and R ⁷ , or R ⁸ and R
Examples of the ring-forming group in ¹⁰ include a trimethylene group, a tetramethylene group, an oxatrimethylene group, an ethylenedioxy group, and the like, which together with an adjacent carbon form a 5- or 6-membered ring. Form.

Examples of the group in which R ⁷ and R ⁸ together form a ring include a trimethylene group, a tetramethylene group, an oxatrimethylene group, an ethylenedioxy group, and the like. To form a 5- or 6-membered ring.

Examples of the group which forms a ring by combining R ⁶ and R ⁹ include groups which form cyclopentadiene, 1,3-cyclohexadiene, furan and the like together with an adjacent carbon.

The optically active group IIIb metal catalyst in the present invention is obtained by mixing a group IIIb metal perfluoroalkane sulfonate, an optically active binaphthol and a base in an inert solvent in the presence or absence of molecular sieve. Prepared by

Group IIIb metal perfluoroalkanesulfonates include perfluoroalkanesulfonic acid IIIb
It is not particularly limited as long as it is a Group III metal salt, and preferably includes Group IIIb metal trifluoromethanesulfonate (hereinafter also referred to as Group IIIb metal triflate), and specifically, lutetium triflate, ytterbium triflate, thulium triflate, erbium triflate , Holmium triflate, dysprosium triflate, terbium triflate, gadolinium triflate, yttrium triflate or scandium triflate. More preferred are scandium triflate and ytterbium triflate.

Optically active binaphthol is [1,1'-
Binaphthalene] -2,2′-diol.

Examples of the base include tertiary amines. Examples thereof include triethylamine, tributylamine, diisopropylethylamine, N-methyldimethylpiperidine,
-Methyltetramethylpiperidine and the like, and preferred are N-methyldimethylpiperidine and N-methyltetramethylpiperidine.

The amount of the optically active binaphthol used is 0.5 to the group IIIb metal perfluoroalkanesulfonate.
２2 molar equivalents, preferably 0.8-1.5 molar equivalents. The amount of the base used is 1.5 to 3 molar equivalents, preferably 1.8 to 2.5 molar equivalents, based on the Group IIIb metal perfluoroalkanesulfonate.

The inert solvent used in the above catalyst preparation reaction includes hydrocarbon solvents such as hexane and benzene, ether solvents such as ethyl ether, tetrahydrofuran and dioxane, acetonitrile, dimethylformamide, dimethylsulfoxide, chloroform and methylene chloride. And the like, preferably methylene chloride.

The temperature for preparing the catalyst is usually from -20 ° C to 4 ° C.
It is 0 ° C, preferably around 0 ° C (-10 to 20 ° C).
The catalyst preparation time is generally 0.1 to 8 hours, preferably 1 to 3 hours.

In the presence of the above-mentioned optically active group IIIb metal catalyst and 1,3-diketone, an olefin represented by the formula (I) (hereinafter also referred to as olefin) and a diene represented by the formula (II) (Hereinafter, also referred to as a diene), to produce an optically active cyclic compound represented by the formula (III). Further, after the preparation of the catalyst, the cyclization reaction can be continuously performed without isolating the catalyst.

The 1,3-diketone is not particularly limited as long as it is a ketone having a carbonyl at the β-position. Examples thereof include acetylacetone, 3-phenylacetylacetone, and 2-
Acetylcyclopentanone and the like, preferably 3
-Phenylacetylacetone and 2-acetylcyclopentanone.

The olefin is not particularly limited as long as it is represented by the formula (I), but is preferably methyl acrylate, methyl crotonate, methyl cinnamate, acrolein,
Methacrolein, 3-acryloyl-1,3-oxazolidin-2-one, 3-crotonoyl-1,3-oxazolidin-2-one, 3-cinnamoyl-1,3-oxazolidin-2-one, acrylonitrile, 3- ( 2-
Hexenoyl) -1,3-oxazolidine-2-one and the like.

The diene is not particularly limited as long as it is represented by the formula (II), but is preferably a cycloalkadiene which may have a substituent (for example, cyclopentadiene, 1,3-cycloalkane). Diene, etc.), alkadiene which may have a substituent (for example, 2-methylbutadiene, 2,3-dimethylbutadiene, etc.), and the like,
More preferred is cyclopentadiene.

The amount of the optically active group IIIb metal catalyst to be used is 0.001 to 1 mol, preferably 0.01 to 0.5 mol, per 1 mol of the olefin. The amount of the 1,3-diketone used is 0.5 to 2 parts of the optically active group IIIb metal catalyst.
It is a molar equivalent, preferably around an equimolar equivalent (0.7 to 1.3 molar equivalent). The diene is used in an amount of 1 molar equivalent or more based on the olefin, and may be used in a solvent amount.

Examples of the solvent include the inert solvents used in the above catalyst preparation reaction. The reaction temperature varies depending on the type of the olefin, the amount of the catalyst, and the like, but is usually from -20 ° C to
The temperature is 40 ° C, preferably 0 ° C to 30 ° C. The reaction time varies depending on the reaction temperature, the amount of the catalyst and the like, but is usually from 10 minutes to
2 days, preferably 1 to 24 hours.

The isolation and purification of the thus obtained optically active cyclic compound from the reaction mixture is carried out in the same manner as the isolation / purification method used in ordinary organic reactions. For example, the reaction is carried out by adding water to the reaction mixture, filtering the formed precipitate, and purifying the filtrate by a usual isolation and purification operation, for example, recrystallization, chromatography and the like.

[0046]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these.

Example 1 Ytterbium triflate 0.1 in an argon atmosphere
To 2 mmol and 125 mg of molecular sieve 4A, 0.12 mmol of 3-phenylacetylacetone was added in 0.1 ml of methylene chloride.
A 5 ml solution was added and stirred at 40 ° C. for 1 hour. After cooling to room temperature, 0.12 mmol of (R)-(+)-binaphthol was added. After cooling to 0 ° C., a solution of 0.24 mmol of N-methyl-2,6-dimethylpiperidine in 1 ml of methylene chloride was added. Stirred for minutes. Then, 3-crotonoyl-1,3-oxazolidin-2-one 0.5 was added to the catalyst solution.
A solution of 0.25 ml of methylene chloride in 0.25 ml of methylene chloride and a solution of 1.5 mmol of cyclopentadiene in 0.25 ml of methylene chloride were added and stirring was continued at 0 ° C. for 20 hours. Water was added to the resulting reaction solution, insolubles were filtered off, and the filtrate was washed with brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give 5-methyl-6- (2-oxo-1,3-oxazolidin-3- having the following physical properties.
Il) carbonyl-2-norbornene was obtained in 69% yield. The endo / exo ratio of this compound was 88/12, and the optical purity of the endo form was 69%. As for the stereochemistry, the main product was the (2R, 3S) form having the opposite stereochemistry to the case where 3-phenylacetylacetone was not added. ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 1.0 (d,
3H, J = 7.0Hz), 1.2-2.1 (m, 3H), 2.46 (brs, 1H), 3.
25 (brs, 1H), 3.48 (dd, 1H), 3.8-4.6 (m, 4H), 5.77
(dd, 1H, J = 2.4, 5.4 Hz), 6.43 (dd, 1H, J = 3.4, 5.4 Hz) IR (neat, cm ^-1 ): 1775, 1698 [α] _D ²⁵ = -148 ° (CCl ₄ )

Example 2 In Example 1, except that 2-acetylcyclopentanone was used instead of 3-phenylacetylacetone,
The reaction and separation and purification were carried out in the same manner as in Example 1 to give 5-methyl-6- (2-oxo-1,3-oxazolidin-3-yl) carbonyl-2-norbornene.
Obtained in 6% yield. The endo / exo ratio of this compound is 81/19, and the optical purity of the endo form is 62% (2
R, 3S-isomer was the main product).

Example 3 A reaction and separation and purification were carried out in the same manner as in Example 1 except that acetylacetone was used instead of 3-phenylacetylacetone, to give 5-methyl-6- (2-oxo). -1,3-Oxazolidin-3-yl) carbonyl-2-norbornene was obtained in a yield of 80%. The endo / exo ratio of this compound was 88/12, and the optical purity of the endo form was 55% (2R, 3S-form is the main product).

Example 4 Ytterbium triflate 0.1 in an argon atmosphere
mmol, 0.12 mmol of (R)-(+)-binaphthol and 125 mg of molecular sieve 4A
The mixture was stirred in ml, N-methyl-2,2,6,6-tetramethylpiperidine (0.24 mmol) was added at 40 ° C, and the mixture was stirred for 3 hours. Then, 0.1 mmol of 3-phenylacetylacetone was added to the reaction solution, and 0.5 mmol of 3-crotonoyl-1,3-oxazolidine-2-one and 0.2 mmol of methylene chloride were added.
A solution of 5 ml and a solution of 1.5 mmol of cyclopentadiene in 0.5 ml of methylene chloride were added and stirring was continued at 0 ° C. for 20 hours. Water was added to the resulting reaction solution, insolubles were filtered off, and the filtrate was washed with brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give 5-
Methyl-6- (2-oxo-1,3-oxazolidine-
3-yl) carbonyl-2-norbornene was obtained with a yield of 83%. The endo / exo ratio of this compound is 93/7
And the optical purity of the endo form is 81% (2R, 3S-
Body was the main product).

Example 5 Example 5 was repeated, except that 0.5 mmol of 3-cinnamoyl-1,3-oxazolidin-2-one was used instead of 0.5 mmol of 3-crotonoyl-1,3-oxazolidine-2-one. Is reacted and separated and purified in the same manner as in Example 4 to give 5-phenyl-6- (2-oxo-
(1,3-oxazolidin-3-yl) carbonyl-2-
Norbornene was obtained in a yield of 51%. En of this compound
The do / exo ratio was 89/11, and the optical purity of the endo form was 83% (2R, 3S-form is the main product). ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 1.2-2.0
(m, 2H), 2.85 (brs, 1H), 3.6-4.4 (m, 5H), 5.80 (d
d, 1H, J = 2.2, 5.4Hz), 6.41 (dd, 1H, J = 2.4, 5.4Hz),
6.9-7.6 (m, 5H) IR (neat, cm ^-1 ): 1770, 1695 [α] _D ²⁵ = + 147 ° (CCl ₄ )

Example 6 In Example 1, 3- (2-hexenoyl) -1,3-oxazolidin-2-one was used instead of 0.5 mmol of 3-crotonoyl-1,3-oxazolidine-2-one.
Except that 5 mmol was used, the reaction and separation and purification were carried out in the same manner as in Example 1 to give 5-propyl-6- (2-oxo-1,3-oxazolidine-3-yl) carbonyl-2-norbornene in 81. % Yield. The endo / exo ratio of this compound was 91/9, and the optical purity of the endo form was 80% (2R, 3S-form is the main product). ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 0.7 (m,
3H), 1.0-1.8 (m, 4H), 2.01 (brs, 1H), 2.63 (brs,
1H), 3.27 (brs, 1H), 3.57 (dd, 1H, J = 2.0, 3.0Hz),
3.8-4.2 (m, 2H), 5.77 (dd, 1H, J = 2.0, 4.0Hz), 6.35
(dd, 1H, J = 2.0, 4.0 Hz) IR (neat, cm ^-1 ): 1775, 1695 [α] _D ²⁵ = + 146 ° (CCl ₄ )

Example 7 The procedure of Example 6 was repeated, except that thulium triflate was used in place of ytterbium triflate. The reaction, separation and purification were carried out in the same manner as in Example 6 to obtain 5-propyl-6- (2-oxo- 1,3-oxazolidine-3
-Yl) carbonyl-2-norbornene was obtained in 85% yield. The endo / exo ratio of this compound was 91/9, and the optical purity of the endo form was 82% (2R, 3S-form was the main product).

Example 8 Example 6 was repeated except that erbium triflate was used instead of ytterbium triflate.
By performing the reaction and the separation and purification in the same manner as described above, 5-propyl-6- (2-oxo-1,3-oxazolidine-
3-yl) carbonyl-2-norbornene was obtained in a yield of 60%. The endo / exo ratio of this compound is 91/9
And the optical purity of the endo form is 85% (2R, 3S-
Body was the main product).

Example 9 A reaction and separation and purification were carried out in the same manner as in Example 5 except that thulium triflate was used instead of ytterbium triflate, to give 5-phenyl-6- (2-oxo- 1,3-oxazolidine-3
-Yl) carbonyl-2-norbornene was obtained in a yield of 51%. The endo / exo ratio of this compound is 89/11
And the optical purity of the endo form is 89% (2R, 3S-
Body was the main product).

Example 10 Example 1 was repeated except that lutetium triflate was used instead of ytterbium triflate.
By performing the reaction and the separation and purification in the same manner as described above, 5-methyl-6- (2-oxo-1,3-oxazolidine-3
-Yl) carbonyl-2-norbornene was obtained in 30% yield. The endo / exo ratio of this compound is 89/11
And the optical purity of the endo form is 51% (2R, 3S-
Body was the main product).

Example 11 A reaction, separation and purification were carried out in the same manner as in Example 1 except that thulium triflate was used instead of ytterbium triflate, to give 5-methyl-6- (2-oxo- 1,3-oxazolidine-3-
Yl) carbonyl-2-norbornene was obtained in a yield of 72%. The endo / exo ratio of this compound was 91/9, and the optical purity of the endo form was 74% (2R, 3S-form is the main product).

Example 12 Example 1 was repeated except that erbium triflate was used in place of ytterbium triflate.
By performing the reaction and the separation and purification in the same manner as described above, 5-methyl-6- (2-oxo-1,3-oxazolidine-3
-Yl) carbonyl-2-norbornene was obtained with a yield of 59%. The endo / exo ratio of this compound is 90/10
And the optical purity of the endo form is 74% (2R, 3S-
Body was the main product).

Example 13 Example 1 was repeated except that holmium triflate was used instead of ytterbium triflate.
By performing the reaction and the separation and purification in the same manner as described above, 5-methyl-6- (2-oxo-1,3-oxazolidine-3
-Yl) carbonyl-2-norbornene was obtained in 70% yield. The endo / exo ratio of this compound is 84/16
And the optical purity of the endo form is 58% (2R, 3S-
Body was the main product).

Example 14 A reaction, separation and purification were carried out in the same manner as in Example 1 except that yttrium triflate was used instead of ytterbium triflate.
Methyl-6- (2-oxo-1,3-oxazolidine-
3-yl) carbonyl-2-norbornene was obtained in 85% yield. The endo / exo ratio of this compound is 91/9
And the optical purity of the endo form is 61% (2R, 3S-
Body was the main product).

Example 15 A reaction, separation and purification were carried out in the same manner as in Example 1 except that gadolinium triflate was used instead of ytterbium triflate.
Methyl-6- (2-oxo-1,3-oxazolidine-
3-yl) carbonyl-2-norbornene was obtained in a yield of 61%. The endo / exo ratio of this compound is 85/1
5, and the optical purity of the endo form was 43% (2R, 3S
-Body was the main product).

Example 16 In Example 1, 1.5 mmol of 1,3-cyclohexadiene was used instead of 1.5 mmol of cyclopentadiene.
Reaction and separation were performed in the same manner as in Example 1 except that 0.5 mmol of 3-acryloyl-1,3-oxazolidin-2-one was used instead of 0.5 mmol of 3-crotonoyl-1,3-oxazolidine-2-one. By performing purification, 5
-(2-oxo-1,3-oxazolidin-3-yl)
Carbonylbicyclo [2.2.2] oct-2-ene was obtained in a yield of 34%. The endo / exo ratio of this compound is 100/0, and the optical purity of the endo form is 66%.
(2R, 3S-isomer is the main product). ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 1.20-1.
30 (m, 2H), 1.50-1.90 (m, 4H), 2.61-2.64 (m, 1H),
2.82-2.85 (m, 1H), 3.72-3.79 (m, 1H), 3.98 (t, 2H,
J = 8.75Hz), 4.36-4.44 (m, 2H), 6.15 (dd, 1H, J = 7.2
5, 7.26Hz), 6.34 (dd, 1H, J = 6.93, 7.26Hz)

[0063]

According to the present invention, an optically active cyclic compound useful as an intermediate for synthesizing a physiologically active substance such as iridoid or eicosanoid can be produced with high optical yield and optical purity. And a compound whose stereochemistry is reversed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification code FI C07M 7:00 C07M 7:00 (58) Field surveyed (Int.Cl. ⁷ , DB name) C07B 37/12 C07B 53/00 C07B 61/00 300 C07D 263/16 B01J 31/22 C01F 17/00 C07M 7:00

Claims (4)

(57) [Claims] An optically active group IIIb metal catalyst and 1,3
-In the presence of a diketone, of the formula (I) (Wherein R ¹ , R ² and R ³ are the same or different,
Each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxyl group, an aralkyloxy group, a protected hydroxyl group, a halogen atom, a cyano group, an alkoxycarbonyl group, an acyl group, an aralkyl group or an aryl group. R ⁴ represents an electron-withdrawing group. R ¹ and R ² , R ³ and R ⁴ ,
Alternatively, R ² and R ⁴ may represent a group forming a ring together. ) And an olefin represented by the formula (II): (Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxyl group, an aralkyloxy group, A hydroxyl group, a halogen atom, a cyano group, a disubstituted amino group, an aralkyl group or an aryl group, which may have a substituent.
R ⁵ and R ^6, R ⁷ and R ^8, R ⁵ and R ^7, R ⁸ and R ^10, R
⁹ and R ¹⁰ or R ⁶ and R ⁹ may together represent a group forming a ring. (III), characterized by reacting with a diene represented by the formula (III): (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ , R ⁹ and R ¹⁰ are as defined above. )). 2. The method for producing an optically active cyclic compound according to claim 1, wherein the diene represented by the formula (II) is a cycloalkadiene which may have a substituent. 3. The method for producing an optically active cyclic compound according to claim 1, wherein the diene represented by the formula (II) is cyclopentadiene. 4. An optically active group IIIb metal catalyst comprising lutetium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, thulium trifluoromethanesulfonate, erbium trifluoromethanesulfonate, holmium trifluoromethanesulfonate, dysprosium trifluoromethanesulfonate,
2. A catalyst prepared from a Group IIIb metal trifluoromethanesulfonate selected from terbium trifluoromethanesulfonate, gadolinium trifluoromethanesulfonate, yttrium trifluoromethanesulfonate or scandium trifluoromethanesulfonate, and an optically active binaphthol and a base. The production method of the optically active cyclic compound described in the above.