JPH0615486B2 - Process for producing optically active 4-hydroxy-2-cyclopentenones - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has the general formula (I) (In the formula, R represents an alkyl group, an alkenyl group or an alkynyl group.) The present invention relates to a novel method for producing an optically active 4-hydroxy-2-cyclopentenone.

Optically active 4-hydroxy- represented by the above general formula (I)
The 2-cyclopentenones are not only useful as pesticides and their intermediates themselves, but also as intermediates for fragrances and pharmaceuticals. For example, when the compound has an S (+) configuration. Can be used as an intermediate of pyrethroid, which is extremely important as a pesticide. When it has an R (-) configuration, it can be used as an important intermediate of a prostaglandin derivative.

Furthermore, these optically active compounds are converted into sulfonic acid esters with, for example, paratoluenesulfonic acid or methanesulfonic acid, and then reacted with a base, or with sodium acetate, sodium dichloroacetate, sodium trichloroacetate, or the like. The corresponding ester may be converted to a corresponding ester and then hydrolyzed to give a 4-hydroxy-2-cyclopentenone having a configuration that is opposite to the original configuration.

Conventionally, as a method for synthesizing the optically active 4-hydroxy-2-cyclopentenone represented by the general formula (I), (A) 2-substituted-4-hydroxy-3-methyl-2-cyclopentenone is used. A method in which compounds are made into half-esters of dicarboxylic acids such as phthalic acid and succinic acid, then resolved using an optically active amine, and further salt-decomposed and hydrolyzed.
-75545, JP-A-50-13366).

(B) Method by asymmetric reduction of ketone (JP-A-54-79252)
issue).

(C) dl-2-allyl-4-hydroxy-3-methyl-
After synthesizing an ether form of 2-cyclopentenone, the ether form of each optical isomer is separated and purified and hydrolyzed (JP-A-54-130556).

(D) A method of hydrolyzing 4-acyloxy-2-allyl-3-methyl-2-cyclopentenone with an enzyme or a microorganism (Japanese Patent Publication No. 56-9917).

Various methods are known.

However, in these known methods, the method (A) is not satisfactory as an industrial production method such that an expensive amine must be used, many treatment steps are required, and complicated operations are required. ) And (C) have various problems such as requiring expensive reagents, complicated operations, and low yield, and method (D) is only an example of the compound and other Nothing is known about the compound, and R (-) obtained by this asymmetric hydrolysis is known.
The optical purity of 2-allyl-4-hydroxy-3-methyl-2-cyclopentenone is not always good, and the R (+)-form, which is more important as a pyrethroid intermediate for agricultural chemicals, is recovered as an ether. Furthermore, there is a problem that it must be hydrolyzed using methanol-sodium methylate or the like, and a complicated operation is required for the subsequent treatment and purification, and any of these methods is satisfactory as an industrial production method. I didn't get it.

From the above, the present inventors have made the optically active 4-hydroxy-2-cyclopentenones of the general formula (I) inexpensive and industrially advantageous, and S (+)-
The present invention has been accomplished as a result of research on a method for obtaining a compound having any configuration of the stereoisomer or the R (-)-configuration in any configuration with high purity and high yield.

That is, the present invention is represented by the general formula (IV) (In the formula, R has the same meaning as described above, provided that the substituent R at the 2-position and the methyl group at the 3-position are in the cis configuration.) The optically active 4-cyclopentenone alcohols Is represented by the general formula
It is a process for producing an optically active 4-hydroxy-2-cyclopentenone represented by (I).

Here, the optically active 4-cyclopentenone alcohols represented by the general formula (IV) are represented by the general formula (III) (In the formula, R has the same meaning as described above, and R ₁ represents an acyloxyl group. However, the substituent R at the 2-position and the methyl group at the 3-position are in cis coordination.) -Or optically active 4-cyclopentenone esters can be obtained by asymmetric hydrolysis using an enzyme or a microorganism. In addition, as one aspect of this method, dl-4-cyclopentenone esters are asymmetrically hydrolyzed using an enzyme or a microorganism, and a general formula (III ^* ), which is a hydrolysis residue, is obtained. (In the formula, R and R ₁ have the same meanings as described above, provided that the substituent R at the 2-position and the methyl group at the 3-position are in cis coordination.) The tenone esters can be separated, and the esters can be hydrolyzed with an enzyme or a microorganism to obtain the optically active 4-cyclopentenone alcohols represented by the general formula (IV).

Further, the dl-4-cyclopentenone esters represented by the general formula (III) are represented by the general formula (II) (In the formula, R has the same meaning as described above, provided that the substituent R at the 2-position and the methyl group at the 3-position are in cis coordination.) And a dl-4-cyclopentenone alcohol It can be obtained by reacting (esterifying) an aliphatic carboxylic acid.

The present invention is also a method for producing the optically active 4-cyclopentenone alcohols represented by the general formula (I) by combining the above respective reactions as shown below.

Hereinafter, the present invention will be described in detail.

The 4-cyclopentenone ester represented by the general formula (III) can be easily and easily obtained by reacting the dl-4-cyclopentenone alcohol represented by the general formula (II) with an aliphatic carboxylic acid. Can be manufactured at a rate.

Here, the dl-4-cyclopentenone alcohol used as a raw material can be easily produced, for example, by rearranging furancarbinol as shown in the following formula, and dl-4-cyclopentenone alcohol The following compounds are illustrated as a class.

3-hydroxy-2,3-dimethyl-4-cyclopentenone, 2-ethyl-3-hydroxy-3-methyl-4-
Cyclopentenone, 3-hydroxy-2-n-propyl-3-methyl-4-cyclopentenone, 2-isopropyl-3-hydroxy-3-methyl-4-cyclopentenone, 3-hydroxy-2-n- Butyl-3-methyl-4
-Cyclopentenone, 2-isobutyl-3-hydroxy-3-methyl-4-cyclopentenone, 3-hydroxy-2-n-pentyl-3-methyl-4-cyclopentenone, 2-isopentyl-3-hydroxy -3-methyl-
4-cyclopentenone, 3-hydroxy-2-n-hexyl-3-methyl-4-cyclopentenone, 3-hydroxy-2-n-heptyl-3-methyl-4-cyclopentenone, 2-allyl- 3-hydroxy-3-methyl-4
-Cyclopentenone, 2- (2-cis-butenyl) -3
-Hydroxy-3-methyl-4-cyclopentenone, 2
-(Ω-butenyl) -3-hydroxy-3-methyl-4
-Cyclopentenone, 2- (2-cis-pentenyl)-
3-hydroxy-3-methyl-4-cyclopentenone,
3-hydroxy-2- (2-trans-pentenyl)-
3-methyl-4-cyclopentenone, 2- (3-cis-
Hexenyl) -3-hydroxy-3-methyl-4-cyclopentenone, 3-hydroxy-2-propargyl-3
-Methyl-4-cyclopentenone, 3-hydroxy-2
-(2-Pentynyl) -3-methyl-4-cyclopentenone, 3-hydroxy-2- (α-methylallyl) -3
-Methyl-4-cyclopentenone.

Examples of the aliphatic carboxylic acids, which are the other raw material, include the following compounds.

Acetic acid, acetic acid chloride, acetic acid bromide, acetic anhydride, propionic acid, propionic acid chloride or bromide, propionic anhydride, butyryl chloride or bromide, caproyl chloride or bromide, caprylic acid chloride or bromide, caprinoyl chloride or bromide, dodecanoin Chloride or bromide, palmitoyl chloride or bromide, chloroacetyl chloride or bromide, dichloroacetyl chloride or bromide.

The reaction of the dl-4-cyclopentenone alcohols with the aliphatic carboxylic acid is carried out by applying a usual esterification condition and reacting with a catalyst in the presence or absence of a solvent.

When a solvent is used in this reaction, as the solvent, for example, tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, hexane or the like aliphatic or aromatic solvent is used. Examples thereof include solvents which are inert to the reaction, such as group hydrocarbons, ethers and halogenated hydrocarbons, alone or in a mixture. The amount used can be used without particular limitation.

Aliphatic carboxylic acids used in the reaction are dl-4 as a raw material.
-It is necessary to have 1 equivalent or more with respect to cyclopentenone alcohols, and the upper limit is not particularly limited, but it is preferably 1 to 4 equivalents.

Examples of the catalyst include organic or inorganic basic substances such as triethylamine, tri-n-butylamine, pyridine, picoline, sodium carbonate, sodium methylate and potassium hydrogencarbonate. The amount used is not particularly limited, but is usually 1 to 5 equivalents relative to the dl-4-cyclopentenone alcohol.

When an organic amine is used as a solvent, the amine may act as a catalyst.

Further, acids such as toluene sulfonic acid, methane sulfonic acid and sulfuric acid can also be used as a catalyst.

The reaction temperature is usually -20 ° C to 150 ° C, preferably -10 ° C to 120 ° C.

The reaction time is not particularly limited.

By such a reaction, dl represented by the general formula (III)
The -4-cyclopentenone esters are obtained easily and in good yields, which are the usual separation means, for example extraction,
Although it can be easily isolated from the reaction mixture by liquid separation, concentration, distillation, etc., the reaction mixture can proceed to the next step as it is.

The optically active 4-cyclopentenone alcohols represented by the general formula (IV) can be obtained by using an enzyme or a microorganism having an ability to hydrolyze the 4-cyclopentenone esters represented by the general formula (III). It is carried out by hydrolyzing either one of the optically active esters. Therefore, the starting 4-cyclopentenone esters used here are not only the dl-form obtained in the previous step, but also the d- or l-form recovered in this reaction, or the d- or l-form.
-It can be used in any form such as an excess of any of the bodies.

As the hydrolase used in this reaction, an enzyme obtained from an animal, a plant, or a microorganism is used, and as its usage form, a purified enzyme, a crude enzyme, an enzyme-containing material, a microorganism culture solution, a culture, a microbial cell, It can be used in various forms such as a culture solution and a product obtained by treating them as needed, and an enzyme and a microorganism can also be used in combination. Alternatively, it can also be used as an immobilized enzyme or immobilized bacterium immobilized on a resin or the like.

Examples of such enzymes include beef liver esterase, pig liver esterase, pig pancreatic esterase, horse liver esterase, dog liver esterase, animal hydrolases such as pig phosphatase, barley, β-amylase obtained from potato, and wheat. Examples of plant hydrolases such as lipase (Wheat Germ, manufactured by Sigma) to be obtained,
Furthermore, microorganisms and lichens belonging to each genus exemplified below,
Examples include microorganisms such as algae and hydrolases obtained from them.

Rhodotorula, Trichoderma, Candida, Hansenula
Genus, Pseudomonas, Bacillus, Achromobacter, No
genus cardia, genus Chromobacterium, genus Flavobacterium, Riz
Opus, Mucor, Aspergillus, Alkaligenes, Tor
ulopsis, Corynebact-erium, Endomyces, Saccar
omyces, Arthrobacter, Metshnikowia, Pleurotu
s, Streptmyces, Proteus, Gliocladi-um, Ace
genus tobacter, genus Helminthosporium, genus Brevibacterium,
Escherichia, Citrobacter, Absidia, Micrococc
Us genus, Pediococcus genus, Klebsiella genus, Geotrichun genus.

Examples of microorganisms belonging to each of these genera include the following.

Rhodotorula minuta IFO-0387, IFO-0412, Rhodotorula
rubra IFO-0870, Rhodotolura minuta var texensis IF
O-0879, Trichoderma longibrachiatum IFO-4847, Cand
ida krusei out-6007 ， Candida cylin-dracea ， Candida
tropicalis PK 233, Candida utilus IFO-1086, Pseud
omonas fragi IFO-3458, Pseudomonas putida IFO-1299
6, Pseudomonas fluorescens IFO-3903, Pseudomonas a
eruginosa IFO-3080, Hansenula anomala var ciferrii
out 6095, Hansenula anomala IFO-0118, Hansenula p
oly morpha IFO-1475, Bacillus cereus IFO-3466, Bac
illus subtilis ATCC-6638, Bacillus pulmilus IFO-12
092, Bacillus subtilis var niger IFO-3108, Achromo
ba-cter lyticus ATCC-21456, Achromobacter parvulus
IFO-13181, Achromobacter sin-plex IFO-12069, Noca
rdia uniformis subtsuyanarenus ATCC-21806, Nocardi
a uniformis IFO-13072, Chromobacterium chocolatum
IFO-3758, Chromobacterium iodinum IFo-3558, Chromo
bacterum viola-ceum IFO-12614, Flavobacterium lute
scens IFO-3084, Flavobacterinm arbonescens IFO-375
0, Flavobacterium heparinum IFO-12017, Flavobacterium
ium capsulatum IFO-12533, Rizopus chinensis IFO-47
68, Mucor pusillus IFO-9856, Aspergillus niger ATC
C-9642, Alkaligenes faecalis IFO-12669, Torulopsis
ernobii IFO-0654, Torulopsis candida IFO-0768, Cor
ynebacterium sepedonicum IFO-13763, Endomyces geot
richum IFO-9542, Saccaromyces carrvisial IFO-033
4, Arthrobacter globiformis IFO-12137, Metschnilco
wia pulcherrima IFO-0561, Pleurotus ostreatus IFO-
7051, Streptomyces grisens IFO-3356, Proteus vulga
ric IFO-3851, Proteus vulgaris IID-874, Gliocladim
roseum IFO-5422, Gliocladium virens IFO-6355, Ace
to bacter aurantius IFO-3247, Helminthosporiumsp A
TCC-20154, Brevibacterium ammoniag-enes IFO-1207
2, Brevibacterium, divari-catum ATCC-14020, Escheri
chia coli IFO-12713, IFO-3302, IFO-13168, Citrobac
ter freundii IFO-12681, Micrococcus varians IFO-37
65, Micrococcusluteus IFO-3066, Pediococcusacidlac
tici IFO-3076, Klebsiella pneumoriae IFO-12059, Ab
sidia hyalospora IFO-8082, Geotrichun candidum IFO
-4597.

In this hydrolysis reaction, since only one optically active substance of the 4-cyclopentenone esters as the raw material is hydrolyzed, d- or l- can be selected by selecting the hydrolase or microorganism to be used. 4-Cyclopentenone alcohols can optionally be obtained.

It is peculiar that any optically active substance of d- or l- can be obtained by such a method, and it is possible to obtain a compound such as 4-cyclopentenone alcohols.
When obtaining a primary alcohol, it can be said that it is extremely difficult to obtain these optically active isomers, considering that they cannot be synthesized by chemical means such as asymmetric reduction because they are tertiary alcohols. According to the asymmetric hydrolysis applied to the invention, 4-cyclopentenone esters can be hydrolyzed with high optical purity, and any active form of optical isomer can be obtained. It is extremely valuable.

Of these 4-cyclopentenone esters, as the enzyme or microorganism for hydrolyzing only the d-form with good optical purity to obtain l-4-cyclopentenone alcohols, for example, the following are particularly preferably used. To be

Pig liver esterase (manufactured by Sigma), Candida siridracea (manufactured by Sigma), Hansenula anomalavar ciferrii
out-6095, Metshnikowia Puleherrima IFO-0561, Pleur
otus Ostreatus IFO-7051, cholesterol esterase (from schizophyllum commune), Candida krusei out
-6007.

As an enzyme or a microorganism for hydrolyzing only the 1-form of 4-cyclopentenone esters with high optical purity to obtain d-4-cyclopentenone alcohol, a microorganism belonging to the genus pseudomonas or a microorganism obtained from this The following enzymes are preferably used.

Pseudomonas fragi IFO-3458, Pseudo-monas flaoresen
s IFO-3903, Pseudomonas aeruginosa IFO-3080 By carrying out such a hydrolysis reaction, only one optically active form of 4-cyclopentenone esters is hydrolyzed to give d- or l-4-cyclopentenone. Alcohols are obtained, and d- which is an unreacted product as a hydrolysis residue.
Form or 1-form or 4-cyclopentenone esters in excess of either of them are obtained, which are l- or d-4-cyclopentenone by hydrolysis by changing the enzyme or microorganism used. Alcohols can be obtained.

For example, if hydrolysis is performed using a microorganism belonging to the genus Pseudomonas or an enzyme obtained therefrom, 4-
Of the cyclopentenone esters, only the 1-form is hydrolyzed to produce d-4-cyclopentenone alcohols, and the other optically active d-form of the raw material remains. D-4-Cyclopentenone esters can be obtained as an unreacted material (hydrolysis residue).

In addition, if hydrolysis is carried out using a microorganism belonging to the genus Candida or an enzyme obtained therefrom, the opposite of the above, 4
-Only the d-form of cyclopentenone esters is hydrolyzed to produce l-4-cyclopentenone alcohols, and l-4-cyclopentenone esters can be obtained as a hydrolysis residue. .

Such a hydrolysis reaction is usually carried out by vigorously stirring the 4-cyclopentenone ester and the above enzyme or microorganism in a buffer solution.

As the buffer solution, a commonly used buffer solution of an inorganic acid salt such as sodium phosphate or potassium phosphate, or a buffer solution of an organic acid salt such as sodium citrate is used, and the pH thereof is 4 to 10, preferably 5. ~ 9, concentration is usually
It is in the range of 0.05 to 2M, preferably 0.05 to 0.5M.

The reaction temperature is usually 20 to 40 ° C., and the reaction time is generally 10 to 70 hours, but it is not limited thereto.

This hydrolysis reaction uses dl-4 as a raw material in terms of optical yield.
When cyclopentenone esters are used, the reaction is preferably completed at less than 50%, and the hydrolysis is preferably completed at an appropriate position depending on the excess ratio of the optically active substance.

After the reaction is completed, in order to separate the hydrolysis product and the hydrolysis residue from the reaction solution, the hydrolysis solution is subjected to extraction treatment with a solvent such as methyl isobutyl ketone, ethyl acetate, ethyl ether, etc., and the solvent is distilled off from the organic layer. After the removal, the concentration residue is further distilled or treated by column chromatography to separate d- or l-4-cyclopentenone alcohols and d- or l-4-cyclopentenone esters, respectively. be able to.

The d- or l-4-cyclopentenone esters recovered here can be further hydrolyzed and used as a raw material for producing a symmetric body.

In addition, depending on the conditions, a part of the asymmetric hydrolysis may be 4
-The following compound in which the 2-position of cyclopentenone alcohols is epi-substituted and the substituent R at the 2-position and the methyl group at the 3-position are in the trans-coordination However, these compounds do not need to be particularly separated, and by rearranging while retaining a steric structure with 4-cyclopentenone alcohol which is a hydrolysis, an optically active general formula (S) having the same configuration ( 4-indicated by I)
This gives hydroxy-2-cyclopentenones.

In the above optically active substance, 1-4-cyclopentenone esters and d-4-cyclopentenone alcohols are not only useful as raw materials for producing the target compound of the present invention, but also, for example, acetic acid. And heated with sodium acetate and with racemization to rearrange to dl-2-substituted-3-methyl-4-acetoxy-4-cyclopentenone, which is further hydrolyzed to dl-2-substituted-
It can also be used as 3-methyl-4-cyclopentenone.

An optically active 4-hydroxy-2- represented by the general formula (I)
Cyclopentenones are produced by rearrangement of optically active 4-cyclopentenone alcohols represented by the general formula (IV) obtained by the above-mentioned method or the like in the presence of a base or a catalyst while maintaining the steric structure. It

Incidentally, the optically active 4-cyclopentenone alcohols represented by the general formula (IV), which are the raw materials of this reaction step, have not been known at all in the past, and Tetrahed only as a dl-form.
Ron, 34 , 2775 (1978) describes that it is a pair of (i).

However, the specific description about each of the pair of (i) optically active substances, the separation is not described at all, and even the possibility thereof is not described.Of course, each separated optically active substance is The possibility of rearrangement while maintaining the steric structure, and the steric coordination of 4-hydroxy-2-cyclopentenones obtained by rearrangement while maintaining the steric property are not known at all.

That is, if 1-4-cyclopentenone alcohols are rearranged while maintaining their steric structure, 4- (cyclopentenone) alcohols having S (+) coordination
It gives hydroxy-2-cyclopentenones, which are extremely useful as pyrethroid intermediates that are pesticides, and from the other d-4-cyclopentenone alcohols, R (-) compounds are similarly prepared. It was first revealed by the present inventors that 4-hydroxy-2-cyclopentenones having a position are provided, and that this compound is extremely useful as a raw material of prostaglandin which is a drug. . From such a thing,
In the present invention, in rearrangement of optically active 4-cyclopentenone alcohols, it is necessary to retain rearrangement while keeping optical purity as high as possible, that is, by minimizing racemization as much as possible. It is necessary to carry out under appropriate conditions with respect to base, catalyst, temperature, etc.

Examples of the solvent used in this reaction include water, tetrahydrofuran, dioxane, acetone, benzene,
Solvents such as aliphatic or aromatic hydrocarbons such as toluene, ethyl acetate, chlorobenzene, peptane, dichloromethane, dichloroethane, diethyl ether, and cyclohexane, ethers, ketones, esters, halogenated hydrocarbons, which are inert to the reaction, alone or as a mixture. Is used.

Examples of the base or catalyst used in this reaction include organic tertiary amines such as triethylamine, N-methylmorpholine, N-methylpiperidine, N, N'-dimethylpiperazine, pyridine and lutidine, metals such as alumina and silica gel. Inorganic bases such as oxides, caustic soda, caustic potash, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium monohydrogenphosphate, and basic buffer solutions such as carbonate buffer solutions are suitable, and these may be used alone or in combination. Used above.

The amount of such a base or catalyst used is not particularly limited, but is usually 0.05 to 60 times by mole with respect to the optically active 4-cyclopentenone alcohol as a raw material, and the organic tertiary amine or basic buffer solution is It can also be used as a solvent.

The reaction temperature is in the range of -20 to 130 ° C and is appropriately selected depending on the solvent, base or catalyst used.

For example, when the reaction is carried out in the absence of water as a solvent, racemization is unlikely to occur, so the reaction can be carried out in the range of -10 to 130 ° C. Further, in the case of an organic tertiary amine-water mixed system, the range of -10 to 90 ° C is preferable, and in the rearrangement reaction with water alone or under strong basicity, -20 ° C to 50 ° C.
The range of ° C is preferred.

The reaction time is not particularly limited.

From the reaction mixture thus obtained, extraction, liquid separation,
General formula to be obtained by general operations such as concentration and distillation
The optically active 4-hydroxy-2-cyclopentenones of (I) can be obtained with high optical purity and high yield.
The optically active 4 which is the target compound of the present application thus obtained
-Hydroxy-2-cyclopentenones include S (+)
Alternatively, the following compounds having R (-) configuration are exemplified.

4-hydroxy-2,3-dimethyl-2-cyclopentenone, 2-ethyl-4-hydroxy-3-methyl-2-
Cyclopentenone, 4-hydroxy-2-n-pentyl-3-methyl-2-cyclopentenone, 2-isopropyl-4-hydroxy-3-methyl-2-cyclopentenone, 4-hydroxy-2-n- Butyl-3-methyl-2
-Cyclopentenone, 2-isobutyl-4-hydroxy-3-methyl-2-cyclopentenone, 4-hydroxy-2-n-pentyl-3-methyl-2-cyclopentenone-2-isopentyl-4-hydroxy -3-methyl-
2-cyclopentenone, 4-hydroxy-2-n-hexyl-3-methyl-4-cyclopentenone, 4-hydroxy-2-n-heptyl-3-methyl-2-cyclopentenone, 2-allyl- 4-hydroxy-3-methyl-2
-Cyclopentenone, 2- (2-cis-butenyl) -4
-Hydroxy-3-methyl-2-cyclopentenone, 4
-Hydroxy-2- (ω-butynyl) -3-methyl-2
-Cyclopentenone, 2- (2-cis-pentenyl)-
4-hydroxy-3-methyl-2-cyclopentenone,
4-hydroxy- (2-trans-pentenyl) -3-
Methyl-2-cyclopentenone, 2- (3-cis-hexenyl) -4-hydroxy-3-methyl-2-cyclopentenone, 4-hydroxy-2-propargyl-3-methyl-2-cyclopentenone, 4-hydroxy-2-
(2-Pentynyl) -3-methyl-4-cyclopentenone, 4-hydroxy-2- (2-methylallyl) -3-
Methyl-2-cyclopentenone.

Next, the present invention will be described with reference to examples.

Example 1 In a flask equipped with a stirrer and a thermometer, 152 g of dl-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone, 1 g of p-toluenesulfonic acid and acetic anhydride 3
Charge 20 g and continue stirring at 100 ° C. for 2 hours. After completion of the reaction, acetic anhydride is distilled off under reduced pressure, and the residue is extracted with toluene. The toluene layer is washed with 1% sodium hydrogen carbonate solution and further washed with water. Toluene was distilled off from the organic layer, and dl-3-
186 g (yield 96%) of acetoxy-2-allyl-3-methyl-4-cyclopentenone was obtained.

(Bp 72-75 ° C / 0.2-0.3 mmHg) dl-3-acetoxy-2-allyl-3-methyl-4-
Cyclopentenone 5 g, Porcine Liver Esterase (Sigma) 300 mg and 0.1 M phosphate buffer (pH 7.0) 2
00m are mixed and stirred at 25 to 30 ° C for 24 hours.

After completion of the reaction, extraction is performed 3 times with 50 m of methyl isobutyl ketone. The solvent was distilled off from the obtained organic layer, and the concentrated residue was purified by column chromatography with a mixed solution of ethyl acetate: toluene = 3: 5 to give 1-2-allyl-3-hydroxy-3-.
Methyl-4-cyclopentenone 1.84 g (yield 47%)
[Optical rotation α] ²⁰ _D ▼ -23.9 ° (c = 1, chloroform),
▲ n ²⁰ _D ▼ 1.4983] and l-3-acetoxy-2-allyl-
2.5 g of 3-methyl-4-cyclopentenone ▲ [Optical rotation α] ²⁰ _D ▼ -91.8 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼
1.4801] was obtained.

Then, the obtained 1-2-allyl-3-hydroxy-3-
Methyl-4-cyclopentenone 0.5g, alumina 10g
And 30 m of benzene are stirred at 50-60 ° C for 6 hours. After completion of the reaction, alumina is separated and further washed twice with 10 m of methanol. The liquids were combined and concentrated, and the residue was purified by column chromatography with a mixed liquid of toluene-ethyl acetate = 5: 2, and S (+)-2-allyl-4-hydroxy-3-methyl-2-cyclopentenone 0.43 g was obtained. The optical purity of this product was 98%.

[Analysis method of optical purity: Agric. Biol. Chem., 41 (10), 200
3-2006 (1977)] Optical rotation ▲ α] ²⁰ _D ▼ + 15.3 ° (c = 1, chloroform) ▲ n ²⁰ _D ▼ 1.5166 Example 2 dl-3-hydroxy-2- (ω-butenyl) in a flask. Charged with 16.6 g of -3-methyl-4-cyclopentenone, 0.2 g of pyridine and 35 g of acetic anhydride, 100 to 120 ° C.
Stir for 3 hours. Hereinafter, post-treatment according to Example 1,
Purified, dl-3-acetoxy-2- (ω-butenyl)
1-3-g-3-methyl-4-cyclopentenone (yield 96
%) Was obtained.

(Bp 81-85 ° C / 0.2 mmHg) dl-3-acetoxy-2- (ω-butenyl) -3-methyl-4-cyclopentenone 2 g, Porcine Liver Este
80 mg of rase (manufactured by Sigma) and 100 m of 0.1 M phosphate buffer aqueous solution (pH 8) are mixed and vigorously stirred at 25 to 30 ° C. for 24 hours.

After completion of the reaction, extraction is performed 3 times with 40 m of methyl isobutyl ketone. Then, post-treatment and purification were carried out according to Example 1, and l-
3-hydroxy-2- (ω-butenyl) -3-methyl-
0.68 g of 4-cyclopentenone (yield 42.6%) ▲ [optical rotation α] ²⁰ _D ▼ -22.5 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.4992] and l-3-acetoxy-2-ω
-Butenyl-3-methyl-4-cyclopentenone 0.97 g
▲ [Optical rotation α] ²⁰ _D ▼ -84.6 ° C (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.4810] were obtained.

0.5 g of 1-3-hydroxy-2- (ω-butenyl) -3-methyl-4-cyclopentenone, triethylamine 1
50 g of alumina, 10 g of alumina and 30 m of benzene
Stir at 0 ° C. for 6 hours. After completion of the reaction, alumina is separated and further washed twice with 10 m of methanol.

The liquids are combined and concentrated, and the residue is toluene-ethyl acetate =
Purify by column chromatography with a mixture of 5: 2, S (+)-4
0.45 g of -hydroxy-2-ω-butenyl-3-methyl-2-cyclopentenone was obtained.

Optical purity 98.1% ▲ α] ²⁰ _D ▼ + 14.8 ° (c = 1, chloroform) ▲ n ²⁰ _D ▼ 1.5174 Example 3 A flask containing dl-3-hydroxy-2-propargyl-
30 g of 3-methyl-4-cyclopentenone and 70 g of acetic anhydride are charged, and the mixture is stirred at 100 to 120 ° C. for 3 hours. After completion of the reaction, post-treatment and purification were carried out according to Example 1, and dl-
3-acetoxy-2-propargyl-3-methyl-4-
36.4 g (yield 95%) of cyclopentenone was obtained.

(Bp 82-86 ° C / 0.2-0.3 mmHg) dl-3-acetoxy-2-propargyl-3-methyl-4-cyclopentenone 2 g, Porcine Liver Esterase
80 mg (manufactured by Sigma) and 80 m of a 0.1 M phosphate buffer aqueous solution (pH 6) are mixed and vigorously stirred at 35 ° C. for 20 hours.

After completion of the reaction, extraction is performed 3 times with 40 m of methyl isobutyl ketone. The solvent was distilled off from the obtained organic layer, and the concentrated residue was purified by column chromatography with a mixed solution of ethyl acetate: toluene = 3: 5 to give l-3-hydroxy-3-methyl-2-.
Propargyl-4-cyclopentenone 0.72 g (yield 46.1
%) ▲ [Optical rotation α] ²⁰ _D ▼ -131.7 ° (c = 1, chloroform), mp 61 ° C.] and l-3-acetoxy-2-propargyl-3-methyl-4-cyclopentenone 0.96 g ▲
[Optical rotation α] ²⁰ _D ▼ -16.2 ° (c = 1, chloroform),
▲ n ²⁰ _D ▼ 1.4943] was obtained.

Next, 0.5 g of l-3-hydroxy-2-propargyl-3-methyl-4-cyclopentenone obtained here was applied to a column of 20 g of silica gel using 3 m of a mixed solution of toluene: ethyl acetate = 5: 2. Adsorb. After 24 hours, the mixture is distilled and purified. 0.30 g of S (+)-4-hydroxy-2-propargyl-3-methyl-2-cyclopentenone is obtained.

Optical purity 97.5% ▲ α] ²⁰ _D ▼ + 21.4 ° (c = 1, chloroform) ▲ n ²⁰ _D ▼ 1.5311 Crystallized when left standing.

Example 4 A flask was charged with dl-3-hydroxy-2-n-pentyl-.
Charged 18.2 g of 3-methyl-4-cyclopentenone, 0.1 g of triethylamine and 36 g of acetic anhydride, 60 to 8
Stir at 0 ° C. for 3 hours. Thereafter, the product was post-treated and purified according to Example 1, and 21.9 g of dl-3-acetoxy-2-n-pentyl-3-methyl-4-cyclopentenone (yield 98
%) Was obtained.

(Bp 100 to 110 ° C./0.1 to 0.3 mmHg) dl-3-acetoxy-2-n-pentyl-3-methyl-4-cyclopentenone 2 g, Porcine Liver Esterase
(Sigma) 100 mg, 0.1 M phosphate buffer aqueous solution (pH 7) 90 m and methanol 10 m are mixed,
Stir vigorously at 35 ° C. for 20 hours.

After completion of the reaction, extraction is performed twice with 30 m of toluene. After that, post-treatment and purification were carried out according to Example 1, and 0.7 g of 1-3-hydroxy-2-n-pentyl-3-methyl-4-cyclopentenone (yield 43.1%) ▲ [optical rotation α] ²⁰ _D ▼ -1
8.4 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.4818] and l
-3-acetoxy-2-n-pentyl-3-methyl-4
-Cyclopentenone (1.04 g) [[Optical rotation α] ²⁰ _D -69.4 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.4708] was obtained.

l-3-hydroxy-2-n-pentyl-3-methyl-
4-cyclopentenone 0.5 g, triethylamine 2 g,
Alumina 10 g and benzene 30 m are added at 60 to 70 ° C.
Stir for 6 hours. Hereinafter, post-treatment according to Example 2,
Purified and S (+)-4-hydroxy-2-n-pentyl-
0.44 g of 3-methyl-2-cyclopentenone was obtained.

Optical purity 97% ▲ α] ²⁰ _D ▼ + 17.9 ° (c = 1, chloroform) ▲ n ²⁰ _D ▼ 1.4888 Example 5 A flask containing dl-3-hydroxy-2,3-dimethyl-
4-Cyclopentenone 12.6g, p-toluenesulfonic acid
Charge 0.5g and acetic anhydride 30g, 80 ~ 100 ℃
Stir for 3 hours. Then, post-treatment and purification were carried out according to Example 2, and dl-3-acetoxy-2,3-dimethyl-4-
16.2 g (yield 96.5%) of cyclopentenone was obtained.

(Bp 52 to 55 ° C./0.4 to 0.5 mmHg) dl-3-acetoxy-2,3-dimethyl-4-cyclopentenone 2 g, Porcine Liver Esterase (manufactured by Sigma) 100 mg and 0.1 M phosphate buffer aqueous solution (pH 7)
Mix 100 m and stir at 25-30 ° C. for 24 hours.

After completion of the reaction, extraction is performed 3 times with 50 m of methyl isobutyl ketone. The solvent was distilled off from the organic layer, and the concentrated residue was purified by column chromatography with a mixture of ethyl acetate: toluene = 3: 5 to give 0.43 g of 1-3-hydroxy-2,3-dimethyl-4-cyclopentenone (yield 31%) ▲ [Optical rotation α] ²⁰ _D ▼ -24.3 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.4765] and l-acetoxy-2,3-dimethyl-4-cyclopentenone 1.24 g ▲ [ Optical rotation α] ²⁰
_D ▼ -20.7 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.469
7] was obtained.

0.3 g of 1-3-hydroxy-2,3-dimethyl-4-cyclopentenone, 3 g of triethylamine and 0.3 g of water are stirred at 30 ° C. for 48 hours. After completion of the reaction, the reaction solution is extracted 3 times with 15 m of methyl isobutyl ketone.

The organic layers are combined and washed with 0.5N hydrochloric acid and water in that order. The organic layer is concentrated, and the residue is purified by chromatography with toluene: ethyl acetate = 5: 3. 0.28 g of S (+)-4-hydroxy-2,3-dimethyl-2-cyclopentenone was obtained.

Optical purity 86% ▲ α] ²⁰ _D ▼ + 19.3 ° (c = 1, chloroform) ▲ n ²⁰ _D ▼ 1.5070 Example 6 dl-3-acetoxy-2-allyl-3-methyl-4-
Cyclopentenone 1 g, esterase (lipase from Wheat Germ manufactured by Sigma) 0.2 g and 0.1 M phosphate buffer 10 m are mixed and stirred at 25 to 30 ° C. for 35 hours. After the reaction was completed, the reaction solution was mixed with methyl isobutyl ketone 1
Extract 3 times at 0 m. The solvent was distilled off from the obtained organic layer, and the concentrated residue was purified by column chromatography with a mixed solution of ethyl acetate: toluene = 3: 5 to give 1-2-allyl-3-hydroxy-3-methyl-4-cyclopentene. 0.18 g of tenone was obtained.

1-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone 0.15 g was added to 0.1 M carbonate buffer 5 m (pH 1
1.5) with 0-5 ° C for 24 hours, then at 20 ° C for 2 hours
Stir for 4 hours. After completion of the reaction, methyl isobutyl ketone 1
Extract 4 times at 0 m. The organic layers are combined and concentrated.
The concentrated residue is purified with a mixed solution of toluene: ethyl acetate = 5: 2. 0.14 g of S (+)-2-allyl-3-methyl-4-hydroxy-2-cyclopentenone was obtained.

The optical purity was 78.7%.

Example 7 200 m of nutrient liquid medium (medium composition: glucose 1%, yeast extract 0.3%, malt extract 0.3%, polypeptone 0.5%, adjusted to pH 5.6) was added to a 500 m Sakaguchi flask,
After sterilization, inoculate Candida Krusei out-6007 for 2 days, 3
Culture was performed with shaking at 0 ° C. Next, dl-3-acetoxy-2-
Allyl-3-methyl-4-cyclopentenone (4 g) is added, and the mixture is subjected to shaking culture at 30 ° C. for 24 hours for hydrolysis. After the reaction, the supernatant obtained by centrifugation is extracted 4 times with 70 m of methyl isobutyl ketone. The solvent was distilled off from the obtained organic layer, and the concentrated residue was purified by column chromatography with a mixed solution of ethyl acetate: toluene = 3: 5 to give 1-2-allyl-3.
-Hydroxy-3-methyl-4-cyclopentenone 1.5
g (yield 48%) [optical rotation-21.7 ° (c = 1, chloroform)] and l-3-acetoxy-2-allyl-3-methyl-
4-Cyclopentenone 1.96 g [optical rotation α] ²⁰ _D- 82.6
(C = 1, chloroform)] was obtained.

0.5 g of 1-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone, 4 m of triethylamine and 0.5 g of water are mixed and stirred at 20 to 30 ° C. for 48 hours. After completion of the reaction, post-treatment and purification according to Example 6 were carried out, and S
(+)-2-Allyl-4-hydroxy-3-methyl-2-
0.46 g of cyclopentenone was obtained.

The optical purity was 89.5%.

Example 8 200 m bacterial medium in 500 m Sakaguchi flask (glucose 1%, yeast extract 0.5%, peptone 0.1%, K ₂ HP
O ₄ 0.05%, pH 7) was added and after sterilization Pseudomonas fragi IF
O-3458 was inoculated and cultured with shaking at 30 ° C. for 2 days. Then dl-3-acetoxy-2-allyl-3-methyl-4-
Cyclopentenone (1.5 g) is added, and the mixture is cultured by shaking at 30 ° C. for 24 hours to perform hydrolysis. This is extracted 4 times with 50 m of methyl isobutyl ketone. The solvent was distilled off from the obtained organic layer, and the concentrated residue was purified by column chromatography with a mixed solution of ethyl acetate: toluene = 3: 5 and d-2-allyl-3.
-Hydroxy-3-methyl-4-cyclopentenone 0.28
g (24% yield) ▲ [Optical rotation α] ²⁰ _D ▼ + 22.5 ° (c =
1, chloroform), ▲ n ²⁰ _D ▼ 1.4978] and d-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone 0.75 g ▲ [optical rotation α] ²⁰ _D ▼ + 80.7 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.4801] was obtained.

0.25 g of d-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone together with 2 m of triethylamine, 5 g of alumina and 20 m of benzene at 50-60 ° C.
Heat for 10 hours. After completion of the reaction, post treatment and purification were carried out according to Example 1 to obtain 0.2 g of R (-)-2-allyl-4-hydroxy-3-methyl-2-cyclopentenone.

Optical purity 94% ▲ α] ²⁰ _D ▼ -141 ° (c = 1, chloroform) ▲ n ²⁰ _D ▼ 1.5158 ° Example 9 dl-3-acetoxy-2-allyl-in Example 8
1-3-acetoxy-2-allyl-3-methyl-4 obtained in Example 1 in place of 3-methyl-4-cyclopentenone
-Reaction, post-treatment and purification were conducted in the same manner as in Example 8 except that 1.25 g of cyclopentenone was used, and 0.59 g of d-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone.
(Yield 60%) ▲ [Optical rotation α] ²⁰ _D ▼ + 23.6 ° (c = 1, chloroform)
▲ n ²⁰ _D ▼ 1.4984] was obtained.

0.5 g of d-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone, 15 g of alumina, 4 m of triethylamine and 25 m of benzene are heated at 50-60 ° C for 8 hours.

Thereafter, post-treatment and purification were carried out according to Example 8, and R (-)-2-
0.42 g of allyl-4-hydroxy-3-methyl-2-cyclopentenone was obtained.

The optical purity was 95%.

Example 10 dl-2-allyl-3-hydroxy-3-methyl-4-
Cyclopentenone (3.1 g) and pyridine (9.3 g) are dissolved in dichloromethane (15.5 g), and octanoyl chloride (7.7 g) is added dropwise thereto at 10 to 20 ° C. over 3 hours. After completion of the dropping, the reaction is continued for 25 hours while keeping the temperature at 20 to 30 ° C. After completion of the reaction, 10 m of water is added while keeping the reaction solution at 10 ° C or lower. The reaction mixture is separated, and the organic layer is further washed successively with 1% hydrochloric acid water, 1% heavy soda water and water. The solvent is distilled off from the obtained organic layer, and the residue is purified by chromatography. Distillation solvent toluene: ethyl acetate = 10: 1,
4.64 g (91%) of dl-2-allyl-3-octanoyloxy-3-methyl-2-cyclopentenone are obtained.

▲ n ²⁰ _D ▼ 1.4757 Next, dl-2-allyl-3-octanoyloxy obtained here instead of dl-3- acetoxy-2-allyl-3-methyl-4-cyclopentenone in Example 8 -3
-Methyl-2-cyclopentenone was reacted and worked up in the same manner as in Example 8 except that 2.0 g of 2-methyl-2-cyclopentenone was used, and l-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone was obtained.
0.3 g was obtained.

0.2 g of 1-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone together with 1.5 m of triethylamine, 4 g of alumina and 15 m of benzene at 50 to 60 ° C.
Heat for 10 hours. Then, post-treatment and purification were carried out in accordance with Example 8 to obtain R (-)-2-allyl-4-hydroxy-3.
0.15 g of methyl-2-cyclopentenone was obtained.

The optical purity was 76%.

Example 11 2 g of dl-3-acetoxy-2-n-pentyl-3-methyl-4-cyclopentenone was added to the culture solution prepared according to Example 8 and hydrolyzed by shaking culture at 30 ° C. for 30 hours. I do. This is extracted twice with 40 m of methyl isobutyl ketone. Then, post-treatment and purification were carried out according to Example 8 to give d-3-hydroxy-2-n-pentyl-3.
-Methyl-4-cyclopentenone 0.48 g (yield 30%)
▲ [Optical rotation α] ²⁰ _D ▼ + 17.5 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.4811] and d-3-acetoxy-2-n
-Pentyl-3-methyl-4-cyclopentenone 0.86g
▲ [Optical rotation α] ²⁰ _D ▼ + 60.8 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.4703] were obtained.

d-3-hydroxy-2-n-pentyl-3-methyl-
4-cyclopentenone 0.4g, triethylamine 4m
And 0.2 g of water are stirred at 30-40 ° C. for 20 hours.
Thereafter, post-treatment and purification were carried out according to Example 7, and R (-)-4-
0.33 g of hydroxy-2-n-pentyl-3-methyl-2-cyclopentenone was obtained.

The optical purity was 88%.

▲ α] ²⁰ _D ▼ -16.3 ° (c = 1, chloroform) ▲ n ²⁰ _D ▼ 1.4879 Example 12 dl-3-acetoxy-2-allyl-in Example 8
Dl-3-instead of 3-methyl-4-cyclopentenone
D-3-Hydroxy-2-propargyl-3-methyl was reacted, worked up and purified in the same manner as in Example 8 except that 1.5 g of acetoxy-2-propargyl-3-methyl-4-cyclopentenone was used. -4-Cyclopentenone 0.19g
(Yield 16%) ▲ [Optical rotation α] ²⁰ _D ▼ + 124 ° (c = 1,
Chloroform), ▲ n ²⁰ _D ▼ 1.5103] and d-3-acetoxy-2-propargyl-3-methyl-4-cyclopentenone 0.82 g ▲ [optical rotation α] ²⁰ _D ▼ + 14.6 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.4943] was obtained.

d-3-hydroxy-2-propargyl-3-methyl-
0.15 g of 4-cyclopentenone was rearranged in the same manner as in Example 3 to give R (-)-4-hydroxy-2-propargyl-3-
0.09 g of methyl-2-cyclopentenone was obtained.

The optical purity was 93%.

▲ α] ²² _D ▼ -19.2 ° (c = 1, chloroform) ▲ n ²⁰ _D ▼ 1.5302 Example 13 The culture solution prepared according to Example 8 was added with dl-3-acetoxy-2-ω-butenyl-3-. Methyl-4-cyclopentenone (2 g) is added, and the mixture is shake-cultured at 30 ° C. for 2 hours for hydrolysis. This is extracted twice with 40 m of methyl isobutyl ketone. Post-treatment and purification were carried out in the same manner as in Example 8 below to give 0.32 g of d-3-hydroxy-2-ω-butenyl-3-methyl-4-cyclopentenone (yield 20%).
[Optical rotation α] ²⁰ _D ▼ + 21.1 ° (c = 1, chloroform), ▲ n ²⁰ _D ▼ 1.4983] and d-3-acetoxy-2-ω-butenyl-3-methyl-4-cyclopentenone 1.02 g ▲ [Opticality α] ²⁰ _D ▼ + 62 ° (c = 1, chloroform), ▲ n ²⁰ _D
▼ 1.4806] was obtained.

d-3-Hydroxy-2-ω-butenyl-3-methyl-
4-cyclopentenone 0.25g, triethylamine 0.5
g, alumina and 15 m of benzene are stirred at 50-60 ° C. for 6 hours. Then, after treatment and purification according to Example 2, R (-)-4-hydroxy-2-ω-butenyl-3 was used.
0.22 g of methyl-2-cyclopentenone was obtained.

Optical purity 92% ▲ α] ²⁰ _D ▼ -13.7 ° (c = 1, chloroform) ▲ n ²⁰ _D ▼ 1.5170 Examples 14 to 16 In place of Candida krusei Out-6007 in Example 7, microorganisms shown in Table-1. Table 1 shows the results of the reaction, post-treatment and purification in the same manner as in Example 7 except that was used.

Examples 17 to 19 Tables instead of Porcine Liver Esterase in Example 1
Table 2 shows the results of the reaction, post-treatment and purification in the same manner as in Example 1 except that the hydrolase described in 2 was used.

Example 20 Instead of Pseudomonas fragi IFO-3458 in Example 8
Using Pseudomonas fluore-sens IFO-3903, and further dl
1-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone obtained in Example 1 in place of -3-acetoxy-2-allyl-3-methyl-4-cyclopentenone 1.
Reaction and purification were carried out in the same manner as in Example 8 except that 0 g was used, and d
0.17 g (yield 22%) of 2-allyl-3-hydroxy-3-methyl-4-cyclopentenone was obtained.

d-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone 0.1 g, alumina 10 g and water 20 m
Is stirred at 20 to 30 ° C for 10 hours and further at 30 to 40 ° C for 10 hours. Alumina is separated and further washed twice with 10 m of methanol. The liquid is concentrated under reduced pressure. The residue is purified by chromatography and R (-)-2-allyl-
4-hydroxy-3-methyl-2-cyclopentenone 0.
8 g was obtained.

The optical purity was 83%.

Examples 21 to 23 Reactions similar to those in Example 14 except that the compounds shown in Table 3 were used instead of dl-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone in Example 14,
The results of post-treatment and purification are shown in Table-3.

Examples 24-27 1-2-Allyl-3-hydroxy-3-obtained in Example 1
Table 4 shows the results of rearrangement of methyl-4-cyclopentenone under the conditions shown in Table 4 to obtain S (+)-2-allyl-4-hydroxy-3-methyl-2-cyclopentenone. .
Post-treatment and purification after completion of the reaction were carried out according to the above-mentioned examples.

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Claims (7)

[Claims] 1. A general formula (In the formula, R represents an alkyl group, an alkenyl group or an alkynyl group, and R ₁ represents an acyloxyl group, provided that the substituent R at the 2-position and the methyl group at the 3-position are in cis coordination.) The represented dl- or optically active 4-cyclopentenone ester is subjected to asymmetric hydrolysis with an enzyme or a microorganism to give a compound of the general formula (In the formula, R has the same meaning as described above, provided that the substituent R at the 2-position and the methyl group at the 3-position are in the cis configuration.) The optically active 4-cyclopentenone alcohols And then rearranges while retaining the three-dimensional structure. (In the formula, R has the same meaning as described above.) A method for producing an optically active 4-hydroxy-2-cyclopentenone. 2. General formula (In the formula, R represents an alkyl group, an alkenyl group, or an alkynyl group. However, the substituent R at the 2-position and the methyl group at the 3-position are in cis coordination.) General formula by reacting tenone alcohols with aliphatic carboxylic acids (In the formula, R has the same meaning as described above, and R ₁ represents an acyloxyl group. However, the substituent R at the 2-position and the methyl group at the 3-position are in cis coordination.) dl-4-cyclopentenone esters are obtained and then asymmetrically hydrolyzed using an enzyme or a microorganism to give a compound of the general formula (In the formula, R has the same meaning as described above, provided that the substituent R at the 2-position and the methyl group at the 3-position are in the cis configuration.) The optically active 4-cyclopentenone alcohols And then rearranges while retaining the three-dimensional structure (In the formula, R has the same meaning as described above.) A method for producing an optically active 4-hydroxy-2-cyclopentenone. 3. General formula (In the formula, R represents an alkyl group, an alkenyl group or an alkynyl group, and R ₁ represents an acyloxyl group, provided that the substituent R at the 2-position and the methyl group at the 3-position are in cis coordination.) An asymmetric hydrolysis of the indicated dl-4-cyclopentenone esters using an enzyme or a microorganism, and a general formula which is a hydrolysis residue. (In the formula, R and R ₁ have the same meanings as described above, provided that the substituent R at the 2-position and the methyl group at the 3-position are in cis coordination.) The tenon esters are separated, and the esters are hydrolyzed using an enzyme or a microorganism to give the general formula (In the formula, R has the same meaning as described above, provided that the substituent R at the 2-position and the methyl group at the 3-position are in the cis configuration.) The optically active 4-cyclopentenone alcohols And then rearranges while retaining the three-dimensional structure (In the formula, R has the same meaning as described above.) A method for producing an optically active 4-hydroxy-2-cyclopentenone. 4. An optically active 4-cyclopentenone alcohol is a 1-form, and an optically active 4-hydroxy-2-
The method according to claims 1, 2 and 3, wherein the cyclopentenones are S (+)-forms. 5. An optically active 4-cyclopentenone alcohol is a d-form, and an optically active 4-hydroxy-2-
The method according to claims 1, 2 and 3, wherein the cyclopentenones are R (-)-forms. 6. An optically active 4-cyclopentenone ester is a d-form, an optically active 4-cyclopentenone alcohol is an l-form, and an optically active 4-hydroxy-2-cyclopene. The method according to claim 1, wherein the tenones are S (+)-forms. 7. An optically active 4-cyclopentenone ester is the 1-form, an optically active 4-cyclopentenone alcohol is the d-form, and an optically active 4-hydroxy-2-cyclopentene. The method according to claim 1, wherein the tenones are R (-)-forms.