JPH07252167A - Production of optically active cyclic compound - Google Patents

Abstract

PURPOSE:To obtain an optically active cyclic compound useful as a synthetic intermediate for physiologically active compound such as ylidoid and eicosanoid by reacting an olefin with a diene in the presence of an optically active group IIIb metal catalyst and a 1,3-diketone. CONSTITUTION:This optically active cyclic compound of formula III can be produced by reacting an olefin of formula I (R<1>, R<2> and R<3> each is H, an alkyl, a cycloalkyl, an alkoxy, an alkenyl, a halogen, cyano, etc.; R<4> is an electron attractive group; R<1> and R<2>, R<3> and R<1> or R<2> and R<3> may together form a ring) with a diene of formula II (R<5> to R<10> each is H, an alkyl, a cycloalkyl, an alkenyl, an alkoxy, a halogen, an aryl, etc.) in the presence of an optically active group Hub metal catalyst and a 1,3-diketone in a solvent (e.g. methylene chloride) at -20 to +40 deg.C for 10 min to 2 days. The catalyst is produced by mixing a group IIIb metal trifluoromethanesulfonate, an optically active binaphthol and a base in an inert solvent. A compound having inverted steric configuration relative to conventional compound can be produced in high optical yield and optical purity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a process for producing an optically active cyclic compound useful as a synthetic intermediate for physiologically active compounds such as iridoids and eicosanoids.

[0002]

2. Description of the Related Art Conventionally, as a method for synthesizing an optically active cyclic compound by a reaction between cyclopentadiene and an olefin, several methods using an optically active Lewis acid catalyst have been proposed. [Journal of the Chemical Society, Chemical Communication (J. Chem. Soc., Chem. Commu
n.), p. 437 (1979); Helv. Chim. 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.), Vol. 111, p. 5340 (19
1989); Journal of the American Chemical
Society (J. Am. Chem. Soc.), 111, 5493 (1989); Tetrahedron asymmetry (Tetrah
edron Asym.), Volume 2, pages 639 (1991); Tetrahedron Asym., Volume 2, 643
Page (1991); Synthesis, page 1 (1991)
Year)) etc.].

As a method using an optically active lanthanoid catalyst, a method using an optically active europium compound which is a nuclear magnetic resonance shift reagent is also known, but its 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.

An object of the present invention is to provide a method for producing an optically active cyclic compound having a steric 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 As a result of intensive studies to achieve the above object, the present inventors have found that 1,3-diketones are allowed to coexist with 1,3-diketones in the production of optically active cyclic compounds. In comparison with the absence of the above, it was found that the reaction proceeds in a high yield even with a catalyst having a low reactivity, and a product in which the stereochemistry is reversed is obtained in a high optical yield, and the present invention has been completed. It was

That is, the present invention is based on the formula (I)

[0008]

[Chemical 4]

(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, R ⁴ represents an electron-withdrawing group, R ¹ and R ² , R ³ and R ⁴ , or R ² and R ⁴ may together represent a group forming a ring), and an olefin represented by the formula (II)

[0010]

[Chemical 5]

(In the formula, 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 or an aralkyloxy group. , A protected hydroxyl group, a halogen atom, a cyano group, a substituted 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. ) With a diene represented by the formula (III), in the presence of an optically active group IIIb metal catalyst and a 1,3-diketone.

[0012]

[Chemical 6]

(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. ) Relates to a method for producing an optically active cyclic compound.

Each symbol used in this specification will be 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, and examples thereof include 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 an alkyl group having 1 to 10 carbon atoms is preferable.

The cycloalkyl group in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ is a cycloalkyl group having 3 to 7 carbon atoms, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group. And the like, and a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group are preferable.

The alkenyl group in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ is a linear or branched alkenyl group having 2 to 20 carbon atoms and having 1 or 2 or more double bonds. ,
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.

Examples of the aralkyloxy group in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ include a benzyloxy group and the like.

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

Examples of the aryl group in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ include a phenyl group and a naphthyl group, and a phenyl group is preferable.

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

The acyl group in R ^{1 to} R ³ is an alkanoyl group having 1 to 20 carbon atoms, an aroyl group or the like, specifically, a formyl group, an acetyl group, a trifluoroacetyl group, a propionyl group, 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, and the disubstituted amino group is a cyclic group. It may be one. Specifically, a dialkylamino group such as a dimethylamino group, a diethylamino group, a diisopropylamino group, a dibenzylamino group or a diaralkylamino group; an alkylarylamino group such as a methylphenylamino group or a benzylphenylamino group or an aralkylarylamino group. 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; imide groups such as phthalimido group and succinimido group. It is.

The above-mentioned groups in R ^{1 to} R ³ and R ^{5 to} R ¹⁰ may have a substituent, as mentioned as some specific examples, and the substituent is 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 above) and the like.

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 and an alkanesulfonyl group. Examples thereof include a group (the alkane portion is the same as the above alkyl group), an arenesulfonyl group (the arene portion is the same as the above aryl group), and the like. Examples of the substituted carbamoyl group include (2-oxo-1,3-oxazolidin-3-yl) carbonyl group and dimethylaminocarbonyl group, and preferably (2-oxo-1,3-oxazolidine-3-yl group. It is a carbonyl group.

The group forming a ring in R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , or R ⁹ and R ¹⁰ is a tetramethylene group, a pentamethylene group, an oxatrimethylene group, Examples thereof include an ethylenedioxy group, which together with adjacent carbons 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, and an ethylenedioxy group, which together with the adjacent carbons 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-membered ring or a 6-membered ring.

Examples of the group in which R ⁶ and R ⁹ combine to form a ring include groups in which adjacent carbons form cyclopentadiene, 1,3-cyclohexadiene, furan and the like.

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

The Group IIIb metal perfluoroalkane sulfonate includes IIIb of perfluoroalkane sulfonic acid.
There is no particular limitation as long as it is a group metal salt, and preferably group IIIb metal trifluoromethanesulfonate (hereinafter, also referred to as group IIIb metal triflate) and the like, 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 means [1,1'-
Binaphthalene] -2,2'-diol is an optically active substance.

Examples of the base include tertiary amines and the like. For example, triethylamine, tributylamine, diisopropylethylamine, N-methyldimethylpiperidine, N
-Methyltetramethylpiperidine and the like are exemplified, and N-methyldimethylpiperidine and N-methyltetramethylpiperidine are preferable.

The amount of the optically active binaphthol used is 0.5 with respect to the Group IIIb metal perfluoroalkane sulfonate.
~ 2 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, relative to the Group IIIb metal perfluoroalkanesulfonate.

Examples of the inert solvent used in the above catalyst preparation reaction include hydrocarbon solvents such as hexane and benzene, ether solvents such as ethyl ether, tetrahydrofuran and dioxane, acetonitrile, dimethylformamide, dimethyl sulfoxide, chloroform and methylene chloride. Etc. are used, and preferably methylene chloride.

The catalyst preparation temperature 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 usually 0.1 to 8 hours, preferably 1 to 3 hours.

Further, in the presence of the above-mentioned optically active group IIIb metal catalyst and 1,3-diketone, the olefin represented by the formula (I) (hereinafter also referred to as olefin) and the diene represented by the formula (II). By reacting with (hereinafter also referred to as a diene), an optically active cyclic compound represented by the formula (III) can be produced. In addition, after the catalyst is prepared, 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, and for example, acetylacetone, 3-phenylacetylacetone, 2-
Acetylcyclopentanone and the like can be mentioned, preferably 3
-Phenylacetylacetone, 2-acetylcyclopentanone.

The olefin is not particularly limited as long as it is represented by the formula (I), but it 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-oxazolidin-2-one and the like.

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

The amount of the optically active group IIIb metal catalyst used is 0.001 to 1 mol, preferably 0.01 to 0.5 mol, based on 1 mol of the olefin. The amount of 1,3-diketone used is 0.5 to 2 of the optically active group IIIb metal catalyst.
It is a molar equivalent, and an equimolar equivalent (0.7 to 1.3 molar equivalent) is desirable. 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 olefin, the amount of catalyst, etc.
It is 40 ° C, preferably 0 ° C to 30 ° C. The reaction time varies depending on the reaction temperature, the amount of catalyst, etc., but is usually 10 minutes to
It is 2 days, preferably 1 to 24 hours.

The isolation / purification of the optically active cyclic compound thus obtained from the reaction mixture is carried out in the same manner as the isolation / purification method used in the usual organic reaction. For example, water is added to the reaction mixture, the formed precipitate is separated by filtration, and the filtrate is purified by usual isolation and purification operations such as recrystallization and chromatography.

[0046]

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

Example 1 Ytterbium triflate 0.1 under argon atmosphere
2 mmol and 125 mg of molecular sieve 4A, 0.12 mmol of 3-phenylacetylacetone in methylene chloride of 0.12.
A 5 ml solution was added and the mixture was stirred at 40 ° C. for 1 hour. After cooling to room temperature, 0.12 mmol of (R)-(+)-binaphthol was added, and 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. Stir for minutes. Then, 3-crotonoyl-1,3-oxazolidin-2-one 0.5
A solution of mmol of methylene chloride in 0.25 ml and a solution of cyclopentadiene of 1.5 mmol in 0.25 ml of methylene chloride were added and stirring was continued at 0 ° C. for 20 hours. Water was added to the obtained reaction solution, the insoluble matter was filtered off, the filtrate was washed with brine, and then 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- having the following physical properties.
Yl) carbonyl-2-norbornene was obtained with a yield of 69%. The endo / exo ratio of this compound was 88/12, and the optical purity of the endo form was 69%. In terms of stereochemistry, the main product was the (2R, 3S) form, which is the opposite of 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, 5.4Hz), 6.43 (dd, 1H, J = 3.4, 5.4Hz) IR (neat, cm ^-1 ): 1775, 1698 [α] _D ²⁵ = -148 ° (CCl ₄ )

Example 2 Example 2 was repeated except that 2-acetylcyclopentanone was used instead of 3-phenylacetylacetone.
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 in 3
Obtained in a yield of 6%. The endo / exo ratio of this compound was 81/19, and the optical purity of the endo body was 62% (2
The R, 3S-form was the main product).

Example 3 5-methyl-6- (2-oxo) was obtained by carrying out the reaction and separation and purification in the same manner as in Example 1 except that acetylacetone was used instead of 3-phenylacetylacetone. -1,3-oxazolidin-3-yl) carbonyl-2-norbornene was obtained with 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 was the main product).

Example 4 Ytterbium triflate 0.1 under argon atmosphere
mmol, (R)-(+)-binaphthol 0.12 mmol and molecular sieve 4A 125 mg, and methylene chloride 1
The mixture was stirred in ml, 0.24 mmol of N-methyl-2,2,6,6-tetramethylpiperidine was added at 40 ° C, and the mixture was stirred for 3 hours. Next, 0.1 mmol of 3-phenylacetylacetone was added to the reaction solution, and 0.5 mmol of 3-crotonoyl-1,3-oxazolidin-2-one was added to 0.2 mmol of methylene chloride.
A 5 ml solution and a solution of cyclopentadiene 1.5 mmol in 0.5 ml methylene chloride were added and stirring was continued for 20 hours at 0 ° C. Water was added to the obtained reaction solution, the insoluble matter was filtered off, the filtrate was washed with brine, and then 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 body is 81% (2R, 3S-
The body was the main product).

Example 5 In Example 4, except that 0.5 mmol of 3-crotonoyl-1,3-oxazolidin-2-one was replaced by 0.5 mmol of 3-cinnamoyl-1,3-oxazolidin-2-one. Was subjected to reaction and separation / purification 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 with a yield of 51%. En of this compound
The do / exo ratio was 89/11, and the optical purity of the endo body was 83% (2R, 3S- body was 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, in place of 0.5 mmol of 3-crotonoyl-1,3-oxazolidin-2-one, 3- (2-hexenoyl) -1,3-oxazolidin-2-one.
By carrying out the reaction and separation and purification in the same manner as in Example 1 except that 5 mmol was used, 81% of 5-propyl-6- (2-oxo-1,3-oxazolidin-3-yl) carbonyl-2-norbornene was obtained. Obtained in% yield. The endo / exo ratio of this compound was 91/9, and the optical purity of the endo form was 80% (2R, 3S- form was 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, 4.0Hz) IR (neat, cm ^-1 ): 1775, 1695 [α] _D ²⁵ = +146 ° (CCl ₄ )

Example 7 5-propyl-6- (2-oxo-) was obtained by carrying out the reaction and separation and purification in the same manner as in Example 6 except that thulium triflate was used instead of ytterbium triflate. 1,3-oxazolidine-3
-Yl) carbonyl-2-norbornene was obtained with a yield of 85%. 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 in Example 6.
5-propyl-6- (2-oxo-1,3-oxazolidine-
3-yl) carbonyl-2-norbornene was obtained with a yield of 60%. The endo / exo ratio of this compound is 91/9
And the optical purity of the endo body is 85% (2R, 3S-
The body was the main product).

Example 9 In the same manner as in Example 5, except that thulium triflate was used instead of ytterbium triflate, 5-phenyl-6- (2-oxo- 1,3-oxazolidine-3
-Yl) carbonyl-2-norbornene was obtained with a yield of 51%. The endo / exo ratio of this compound is 89/11
And the optical purity of the endo body is 89% (2R, 3S-
The body was the main product).

Example 10 Example 1 was repeated except that lutetium triflate was used instead of ytterbium triflate.
5-methyl-6- (2-oxo-1,3-oxazolidine-3 by reacting and separating and purifying in the same manner as
-Yl) carbonyl-2-norbornene was obtained with a yield of 30%. The endo / exo ratio of this compound is 89/11
And the optical purity of the endo body is 51% (2R, 3S-
The body was the main product).

Example 11 5-methyl-6- (2-oxo-) was obtained by carrying out the reaction and separation and purification in the same manner as in Example 1 except that thulium triflate was used instead of ytterbium triflate. 1,3-oxazolidine-3-
Yl) carbonyl-2-norbornene was obtained with 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 was the main product).

Example 12 Example 1 was repeated except that erbium triflate was used instead of ytterbium triflate.
5-methyl-6- (2-oxo-1,3-oxazolidine-3 by reacting and separating and purifying in the same manner as
-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 body is 74% (2R, 3S-
The body was the main product).

Example 13 Example 1 was repeated except that holmium triflate was used instead of ytterbium triflate.
5-methyl-6- (2-oxo-1,3-oxazolidine-3 by reacting and separating and purifying in the same manner as
-Yl) carbonyl-2-norbornene was obtained with a yield of 70%. The endo / exo ratio of this compound is 84/16
And the optical purity of the endo body is 58% (2R, 3S-
The body was the main product).

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

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

Example 16 In Example 1, 1.5 mmol of 1,3-cyclohexadiene was used in place of 1.5 mmol of cyclopentadiene,
Reaction and separation were conducted 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-oxazolidin-2-one. 5 by purifying
-(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 body is 66%.
(2R, 3S-form was 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]

INDUSTRIAL APPLICABILITY According to the present invention, an optically active cyclic compound useful as a synthetic intermediate for physiologically active substances such as iridoids and eicosanoids can be produced with a high optical yield and optical purity. It is possible to produce a compound whose stereochemistry is reversed.

Claims (4)

[Claims] 1. An optically active group IIIb metal catalyst and 1,3
-In the presence of a diketone, a compound of formula (I) (In the formula, 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, and these are substituted. It may have a group, and R ⁴ represents an electron-withdrawing group. In addition, R ¹ and R ² , R ³ and R ⁴ ,
Alternatively, R ² and R ⁴ may together represent a group forming a ring. ) And an olefin represented by the formula (II): (In the formula, 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 or a protected group. And a hydroxyl group, a halogen atom, a cyano group, a substituted 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. ) A diene represented by the formula (III): (In the formula, 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. The manufacturing method of the optically active cyclic compound represented by these. 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. The optically active group IIIb metal catalyst is lutetium trifluoromethane sulfonate, ytterbium trifluoromethane sulfonate, thulium trifluoromethane sulfonate, erbium trifluoromethane sulfonate, holmium trifluoromethane sulfonate, dysprosium trifluoromethane sulfonate,
A catalyst prepared from a group IIIb metal trifluoromethanesulfonate selected from terbium trifluoromethanesulfonate, gadolinium trifluoromethanesulfonate, yttrium trifluoromethanesulfonate or scandium trifluoromethanesulfonate, an optically active binaphthol and a base. A method for producing the optically active cyclic compound described.