JP2003313147A - Optically active adamantane derivative and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new optically active adamantane derivative which can be a raw material for an agrochemical and a medicine, and a raw material for a ferroelectric liquid crystal, or the like, and to provide a method for producing the adamantane derivative. <P>SOLUTION: The optically active adamantane derivative is represented by formulas (I-a), (I-b) and (I-c) [wherein, R<SP>1</SP>is an alkyl group, phenyl group, naphthyl group or a heteroatom-containing aromatic group; R<SP>3</SP>is a halogen atom, hydroxy group, an alkoxy group, an acyl group, an alkylmercapto group or an alkylamino group; R<SP>2</SP>, R<SP>4</SP>and R<SP>5</SP>are each an alkyl group; and (*) represents an asymmetric carbon]. The method for producing the optically active adamantane derivative by way of 7-methylenebicyclo[3.3.1]nonan-3-one is provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel optically active adamantane derivative and a method for producing the same. More specifically, the present invention relates to a novel optically active adamantane derivative that can be used as a raw material for agricultural drugs, ferroelectric liquid crystals and the like, and a method for efficiently producing this derivative via a specific compound.

[0002]

2. Description of the Related Art Optically active substances have the same chemical structure, but their three-dimensional structures are mirror images of each other, such as right and left hands.
There are many substances that can never be overlaid and exhibit different properties, especially in terms of physiological activity. This optically active substance includes a D-form (R-form and + -form) having right-handedness and an L-form (S-type) having left-handedness due to the difference in optical rotation.
The body obtained by ordinary chemical synthesis is a racemic body in which these are mixed in substantially equal amounts. The optical properties of this racemic compound are negated, but an optically active substance can be obtained by dividing it by some method. A substance having one of these three-dimensional structures is called an enantiomer (enantiomer). Optically active substances have the same physicochemical properties, such as solubility and melting point,
In many cases, the physiological activities of the body are significantly different. For example, in the case of general glutamate as a umami seasoning, we feel umami only in the L form, and the D form has a slight sweetness and does not feel umami. These differences in physiological activity are important problems in medicine and pesticides. Particularly in medicine, the problem becomes serious because it is concerned with safety for humans.

Many pharmaceuticals are foreign to the living body,
Even if no side effects are observed, the minimum dose required to return from the abnormal state of the disease to the normal state should be administered for the required period. Therefore, in recent years, a drug having an asymmetric center in the structure of a drug is a racemic compound in which one enantiomer does not show any pharmacological activity on the living body, but only the enantiomer that is suitable for the purpose by optical resolution. It has become highly desirable to provide. On the other hand, in the field of agrochemicals, there is a strong demand for agricultural chemicals that have high activity and high selectivity, use only a small amount, and have a small impact on the environment. It seems to proceed. Furthermore, an optically active substance is also indispensable for a ferroelectric liquid crystal, which is regarded as a promising next-generation liquid crystal display.

As a method for producing such an optically active substance, an asymmetric synthesis method in which only one enantiomer is selectively synthesized and an equal mixture (racemate) of two enantiomers obtained by ordinary synthesis are used. It can be roughly divided into methods for optical division. The former asymmetric synthesis methods include biochemical methods utilizing enzymes and microorganisms, asymmetric catalytic synthesis methods and methods utilizing asymmetric reactions, and the latter optical resolution methods include diastereomer methods. , Preferential crystallization method, chromatography method, clathrate compound method, biochemical resolution method and the like.

By the way, adamantane has a structure in which four cyclohexane rings are condensed in a cage shape, has high symmetry, and is a stable compound. Since its derivative exhibits a unique function, It is known to be useful as a raw material for highly functional industrial materials. For example, since it has optical characteristics and heat resistance, it has been attempted to be used for an optical disk substrate, an optical fiber, a lens or the like (Japanese Patent Laid-Open Nos. 6-305044 and 9-3).
02077 publication).

[0006] When this adamantane derivative is used as a raw material for agricultural medicine or the like, it is desirable to introduce an asymmetric site during its synthesis to obtain an optically active compound, in order to express physiological activity. Heretofore, a method for producing an optically active adamantane derivative by introducing an asymmetric site into an adamantane skeleton has not been studied so far, and an enzymatic reduction method [“J. Chem. Soc., Perkin. Trans.”, No. 1 Volume, p. 317 (1992)], and the fact is that no simple and efficient manufacturing technique has been developed.

Under the circumstances, the present invention provides a novel optically active adamantane derivative which can be used as a raw material for agricultural drugs, ferroelectric liquid crystals and the like, and a method for producing the same in a simple and efficient manner. It is intended to provide.

[0007]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventor achieved the object by passing through a certain compound and utilizing an asymmetric reaction. I found that I could do it. The present invention has been completed based on such findings. That is, the present invention provides (1) the general formula (Ia).

[0008]

[Chemical 4]

(Where R is¹Is an alkyl group, a phenyl group,
Naphthyl group or heteroaromatic group, R ³Is a halogen source
Child, hydroxyl group, alkoxyl group, acyl group,
A kilmercapto group or an alkylamino group is shown. )
And has less asymmetric carbon represented by *
Light, characterized in that one of them has optical activity
Academically active adamantane derivative, (2) general formula (Ib)

[0010]

[Chemical 5]

(Wherein R ² represents an alkyl group, and R ¹ and R ³ are the same as above), and an optically active adamantane derivative (3).
General formula (I-c)

[0012]

[Chemical 6]

(Wherein R ⁴ and R ⁵ each represent an alkyl group, which may be the same or different, and R ³ is the same as the above). An optically active adamantane derivative,
(4) 7-methylenebicyclo [3.3.1] nonane-3
A method for producing an optically active adamantane derivative, characterized in that (5) 7-methylenebicyclo [3.3.1] nonan-3-one is used. The present invention provides a method for producing an optically active adamantane derivative according to (1), (2) or (3).

BEST MODE FOR CARRYING OUT THE INVENTION The optically active adamantane derivative of the present invention is a novel compound listed in the literature, and has the general formula (I-
a)

[0014]

[Chemical 7]

(Wherein R¹Is an alkyl group, a phenyl group,
Naphthyl group or heteroaromatic group, R ³Is a halogen source
Child, hydroxyl group, alkoxyl group, acyl group,
A kilmercapto group or an alkylamino group is shown. )
And has less asymmetric carbon represented by *
A compound of which one site has optical activity, a compound of the general formula (I
-B)

[0016]

[Chemical 8]

(Wherein R ² represents an alkyl group, and R ¹ and R ³ are the same as above), and a compound of the general formula (Ic)

[0018]

[Chemical 9]

(Wherein R ⁴ and R ⁵ each represent an alkyl group, which may be the same or different, and R ³ is the same as the above). Is. In R ¹ in the general formula (Ia) and the general formula (Ib), the alkyl group preferably includes an alkyl group having 1 to 20 carbon atoms. This alkyl group may be linear, branched or cyclic. Examples of the heteroaromatic group include benzofuryl group, benzothienyl group, indolyl group, quinolyl group and the like. Further, the phenyl group, the naphthyl group and the above-mentioned heteroaromatic group may have one or more suitable substituents introduced on the ring.

In R ³ in the above general formulas (Ia), (Ib) and (Ic), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and an alkoxyl group. Preferred examples thereof include an alkoxyl group having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, various butoxy groups, and various pentoxy groups. Also,
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group. Further, the alkylmercapto group is an alkylmercapto group having 1 to 5 carbon atoms, and the alkylamino group is 1 carbon atoms.
Preferable examples thereof include an amino group in which the alkyl group of to 5 is mono-substituted and a di-substituted amino group. Examples of the alkyl group having 1 to 5 carbon atoms in the alkylmercapto group and the alkylamino group include a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups and the like.

As the alkyl group represented by R ² , R ⁴ and R ⁵ in the general formula (Ib) and the general formula (Ic), an alkyl group having 1 to 5 carbon atoms is preferably mentioned. it can. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, and the like as described above. As the optically active adamantane derivative represented by the general formula (Ia), one example is the compound represented by the formula (Ia-1).

[0022]

[Chemical 10]

(+)-1-hydroxy-2-benzylidene-5-chloroadamantane represented by the formula (* represents an asymmetric carbon) is represented by the general formula (Ib). As the optically active adamantane derivative, for example, the compound represented by the formula (Ib-1)

[0024]

[Chemical 11]

(+)-1-hydroxy-2- represented by
(Α-phenylethyl) -5-chloroadamantane,
As the optically active adamantane derivative represented by the general formula (Ic), for example, the compound represented by the formula (Ic-1)

[0026]

[Chemical 12]

(-)-1-hydroxy-3-represented by:
Mention may be made of chloro-4-dimethylaminoethyl adamantane. The general formula (Ia) and the general formula (I-
The method for producing the optically active adamantane derivative represented by b) and the general formula (Ic) is not particularly limited, but according to the method of the present invention shown below, the optically active adamantane derivative can be simply and efficiently produced. Can be manufactured. The method for producing the optically active adamantane derivative of the present invention is represented by the formula (II)

[0028]

[Chemical 13]

7-methylenebis [3.3.1] represented by
The optically active adamantane derivative represented by the general formula (Ia) and the general formula (Ib) is a method of using an asymmetric aldol reaction as shown below. Can be manufactured by
Further, the optically active adamantane derivative represented by the general formula (Ic) can be produced by utilizing an asymmetric epoxidation reaction as shown below. In addition,
The 7-methylenebis [3.3.1] nonan-3-one represented by the formula (II) can be prepared by a known method [“Bull.Chem.Soc.Jpn”,
Volume 74-2, Pages 339-346 (2001
Year)], for example, by reacting 1,3-dibromoadamantane with sodium hydroxide in dioxane at a high temperature, the yield can be about 70%. First, with respect to a preferable method for producing the optically active adamantane derivative represented by the general formula (Ia) and the general formula (Ib),

[0030]

[Chemical 14]

(Wherein Ph is a phenyl group, Me is a methyl group, MX is an alkali metal halide, R ¹ ,
R ² and R ³ are the same as above. ). 7-Methyltonbicyclo [3.3.1] nonane-3 in a suitable solvent such as tetrahydrofuran, diethyl ether, dioxane, hexane and the like.
It is an optically active amine (R, R) -N in the presence of an alkali metal halide, for example, lithium chloride, lithium bromide, sodium chloride, etc., preferably in an amount of 2 to 10 times the equivalent of the one-II. , N-bis (α-methylbenzyl) amine and an amide derived from an alkyllithium such as ethyllithium or butyllithium are added to give -20 to-
The treatment is performed at a temperature of about 100 ° C, preferably -40 to -80 ° C. Then, an aldehyde (R ¹ CHO) is added at the same temperature, and the aldehyde is added to the α-position of the ketone by an asymmetric aldol reaction to produce an optically active ketol compound (III).

At this time, as R ¹ CHO (R ¹ is the same as above), various aldehydes such as octyl aldehyde, benzaldehyde and naphthaldehyde can be used. Next, the above ketol compound (III)
The elimination of the alcohol moiety of the is carried out, for example, by subjecting the hydroxyl group to mesitylation of the hydroxyl group and then treating with a base such as 1,8-diazabicyclo [5.4.0] -7-undecene (DBU). It can be carried out. By this elimination reaction, an alkylidene ketone body (IV) is obtained.

The alkylidene ketone body (IV) thus obtained is cyclized by a known method and R ³
By introducing a group, an optically active adamantane derivative represented by the general formula (Ia) can be obtained. When a chlorine atom is introduced at the same time as the cyclization, titanium tetrachloride can be used. When a hydroxyl group is introduced at the same time as the cyclization, "J.Org.Chem.USSR", No. 1333-
1337 (1985), when introducing an alkoxyl group, "Chem.Acta", Volume 59, 1953-.
1962 (1976), when introducing an acyl group, "J.Org.Chem.USSR", Vol. 27-5, 856.
~ 861 (1991), "Chem. Ber.", 98, 38, when introducing an alkyl mercapto group.
Pp. 88-3891 (1965), "Bull. Chem. Soc. Jpn.", 46, when introducing an alkylamino group.
The method reported in Volume-2, pages 673-674 (1973) can be used.

On the other hand, the above-mentioned alkylidene ketone body (IV)
Is alkylated to obtain a 1,4-adduct (V), which is then cyclized in the same manner as described above and an R ³ group is introduced to give an optically active compound represented by the general formula (Ib). An adamantane derivative is obtained. The above reaction can be carried out at normal pressure throughout the steps. Next, the general formula (I-c)
For a suitable production method of the optically active adamantane derivative represented by

[0035]

[Chemical 15]

(Wherein Piv is a pivaloyl group, Me is a methyl group, and R ³ , R ⁴ and R ⁵ are the same as above). 7-methylenebicyclo [3.3.1] nonane-3- in a suitable solvent such as benzene, hexane, methylene chloride, chloroform and the like.
After reducing the ketone moiety of on (II), it is esterified with pivaloyl chloride or the like, and then the olefin moiety is epoxidized with m-perbenzoic acid or the like to obtain an epoxy compound (VIII). Next, the epoxy compound (V
After the rearrangement of (I) to the allyl alcohol derivative (VII), the allyl alcohol derivative (VII) is treated with L-diisopropyl ditartrate, tetraisopropoxy titanium and t-butyl hydroperoxide in the presence of molecular sieves at room temperature to room temperature. The asymmetric epoxidation reaction is carried out at a temperature of about -50 ° C, preferably 0 to -40 ° C, and the optically active epoxy compound (VII) is produced by kinetic optical resolution, and the optically active allyl alcohol compound (IX ) Get.

Next, the optically active allyl alcohol derivative (IX) was converted into a dialkylacetamide dimethyl acetal [MeC (OMe) ₂ N (R ⁴ ) (R ⁵ ), R ⁴ and R ^4].
5 is the same as above. ] And the like to acetamido to obtain a tertiary amide body (X), and then the ketone moiety is reduced and then oxidized to obtain an aminoketone body (XI).
The thus-obtained aminoketone body (XI) is cyclized by the same method as described above and an R ³ group is introduced to give an optically active adamantane derivative represented by the general formula (Ic). Is obtained. The above reaction can be carried out at normal pressure throughout the steps.

[0038]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 Preparation of (+)-1-hydroxy-2-benzylidene-5-chloroadamantane (Ia-1) 7-methylenebicyclo [3.3.1] nonan-3-one (II) in tetrahydrofuran. ) In the presence of 2 equivalents of lithium chloride per 1 mmol, (R, R)-
After adding amide generated from N, N-bis (α-methylbenzyl) amine and butyllithium and treating at −78 ° C., benzaldehyde was added at the same temperature to give two addition isomers of 71% and 8%, respectively. Obtained in% yield.

The main product was (α-S, β-R) -β-ketol [R ¹ in (III) is a phenyl group], and the optical purity was 74% ee. Then, this was recrystallized from petroleum ether to obtain a pure frame β-ketol compound in a yield of 56% (mp 102 to 103 ° C).
Next, the above β-ketol form is mesitylated and then 1.
By treatment with 8-diazabicyclo [5.4.0] -7-undecene (DBU), a single benzylidene ketone body [(IV) in which R ¹ is a phenyl group] was obtained (mp 102 ° C., optical purity > 99% ee).

Finally, the above benzylidene ketone compound was cyclized with 35 mol% titanium tetrachloride in methylene chloride to give (+)-1-hydroxy-2-benzylidene-5-chloroadamantane (Ia). -1) was obtained with a yield of 86%. Properties of this compound (Ia-1),
The spectroscopic data is shown below. (1) mp: 124 to 126 ° C. (2) Specific optical rotation [α] _D ²⁶ : +49.2 (c0.40,
CHCl ₃ ) (3) Infrared analysis [IR (film)]: ν3366c
m ⁻¹ (4) Nuclear magnetic resonance spectroscopy (NMR) analysis ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 7.31 (t, J = 7.2 Hz,
2H), 7.21 (t, J = 7.2Hz, 1H), 7.15 (d, J = 7.2Hz, 2H), 6.
53 (s, 1H), 3.40 (m, 1H), 2.40 (m, 1H), 2.29 (d, J = 11.3H
z, 1H) 2.24 (d, J = 11.3Hz, 1H), 2.15 (s, 2H), 2.09 (s, 2
H), 1.91 (dt, J = 8.7,1.9Hz, 1H) 1.90-1.81 (br s, 1H),
1.82 (t, J = 8.7Hz, 1H), 1.68 (ddd, J = 13.0,5.0,3.0Hz,
1H), 1.63 (d, J = 13.0Hz, 1H)) ¹³ C-NMR (75MHz, CDCl ₃ ) δ = 147.5, 137.4, 128.
7, 128.2, 126.4, 117.1, 73.2, 66.7, 56.2, 47.4, 4
5.8, 45.5, 36.3, 35.0, 32.2. (5) Mass spectrum (MS): m / z = 274
(M ⁺ ), 274 (100%) (6) High resolution mass spectrometry (HRMS): Calcd for C ₁₇
H ₁₉ ClO (M ⁺ ) = 274.1124 Found = 274.1137

Example 2 (+)-1-hydroxy-2- (α-phenylethyl)
Production of -5-chloroadamantane (Ib-1) In tetrahydrofuran, the benzylidene ketone body produced in Example 1 (in (IV), R ¹ is a phenyl group), trimethylsilyl chloride, hexamethylphosphoric triamide 1,4 by reacting methyllithium with a cuprate reagent formed from cuprous bromide dimethyl sulfide complex in the presence of
An adduct [in the (V), R ¹ is a phenyl group, R ² is a methyl group] was obtained as a single product (mp 86-87).
C). Then, in methylene chloride, the 1,2-adduct was cyclized with 5 mol% titanium tetrachloride at -30 ° C to give a single (+)-1-hydroxy-2.
-(Α-Phenylethyl) -5-chloroadamantane (Ib-1) was quantitatively obtained.

The physical properties and spectral data of this compound (Ib-1) are shown below. (1) Specific rotation [α] _D ²⁹ : +71.3 (c0.52
CHCl ₃ ) (2) Infrared analysis [IR (film)]: ν3448c
m ⁻¹ (3) NMR analysis ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 7.32-7.26 (m, 2H),
7.21-7.16 (m, 3H), 3.01 (dq, J = 9.5,6.8Hz, 1H), 2.56
(d, J = 11.8Hz, 1H), 2.26-2.22 (m, 1H), 2.03-1.91 (m, 4
H), 1.81-1.68 (m, 4H), 1.55-1.53 (m, 1H), 1.48 (d, J =
6.9 Hz, 3 H) ¹³ C-NMR (75 MHz, CDCl ₃ ) δ = 147.2, 128.5, 127.
5, 126.0, 74.1, 67.8, 53.8, 49.8, 47.2, 46.6, 40.
7, 40.5, 35.9, 34.9, 32.4, 24.5 (4) MS: m / z = 290 (M ⁺ ), 105 (100
%) (5) HRMS: Calcd for C ₁₈ H ₂₃ ClO (M ⁺ ) =
290.1437 Found = 290.1432

Example 3 Preparation of (-)-1-hydroxy-3-chloro-4-dimethylaminoethyladamantane (Ic-1) In methylene chloride, 7-methylenebicyclo [3.
3.1] 1 mmol of nonan-3-one (II) was -78
After reduction with diisobutylaluminum hydride at 91 ° C (yield 91%), a catalytic amount of dimethylaminepyridine was added in the presence of triethylamine, and pivaloyl chloride was added to give a pivalate ester (yield 67%). Then, the olefin moiety was epoxidized with m-perbenzoic acid in the presence of sodium hydrogen carbonate to obtain a single epoxidized product (VI). This product was stirred as it was at 30 ° C. for 2 hours to be transferred to the allyl alcohol derivative (VII) (yield 84%).

Then, this allyl alcohol compound (VII)
Molecular sieves 3A in methylene chloride
Under coexistence, at −20 ° C., 15 mol% L-diisopropyl tartrate, 10 mol% tetraisopropoxy titanium, 65
Optically active epoxy compound (VIII) is produced by kinetic optical resolution with mol% t-butyl hydroperoxide, and an optically active allyl alcohol compound (IX) having an optical purity of 96% ee is obtained in a yield of 38%. Obtained. Then, in diphenyl ether, the above allyl alcohol compound (IX)
Is reacted with dimethylacetamide dimethyl acetal at 280 ° C. under reflux to give a single tertiary amide compound [(X) in which R ⁴ and R ⁵ are methyl groups] (mp 80 to 81 ° C.) in a yield of 94%. Got with. Then, in tetrahydrofuran, the above-mentioned tertiary amide compound is reduced with lithium aluminum hydride to lead to an amino alcohol compound, and then, in an acetonitrile / methylene chloride solvent, in the presence of N-methylmorpholine-N-oxide, a catalytic amount of a peroxidic catalyst is used. Oxidation with tetrapropylammonium ruthenate gave an aminoketone product [(XI) in which R ⁴ and R ⁵ were methyl groups].

Finally, in methylene chloride, the above aminoketone was cyclized with titanium tetrachloride at 0 to 30 ° C. for 2 hours to give a single (-)-1-hydroxy-3-.
Chloro-4-dimethylaminoethyl adamantane (I-
c-1) was obtained with a yield of 62%. This compound (I-c-
The physical properties and spectral data of 1) are shown below. (1) mp: 75 to 77 ° C. (2) Specific optical rotation [α] _D ²⁹ : −36.7 (c0.4, C
HCl ₃ ) (3) Infrared analysis [IR (film)]: ν3358c
m ^-1 (4) NMR analysis ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 2.31 (d, J = 7.5 Hz, 1
H), 2.29 (t, J = 7.8Hz, 1H), 2.40 (m, 1H), 2.29 (d, J = 1
1.3Hz, 1H), 2.24 (s, 6H), 2.15 (s, 2H), 2.18 (s, 2H), 2.2
1-2.14 (m, 2H), 2.14-2.05 (m, 1H), 1.90-1.81 (br s, 1H),
1.84 (br.s, 1H), 1.82-1.68 (m, 6H), 1.54-1.46 (m, 1H),
1.29 (dd, J = 13.6,2.4Hz, 2H) ¹³ C-NMR (100MHz, CDCl ₃ ) δ = 72.3, 69.8, 58.6,
57.0, 48.6, 45.6, 45.5, 44.0, 40.8, 34.5, 32.1, 2
8.5, 26.3 (5) MS: m / z = 257 (M ⁺ ), 58 (100
%) (6) HRMS: Calcd for C ₁₄ H ₂₄ ClNO (M ⁺ ).
= 257.1546 Found = 257.1530

[0046]

Industrial Applicability According to the present invention, it is possible to provide a novel optically active adamantane derivative which can be used as a raw material for agricultural drugs, ferroelectric liquid crystals and the like. Further, the above-mentioned optically active adamantane derivative is 7-methylenebicyclo [3.3.
1] By using an asymmetric aldol reaction or an asymmetric epoxidation reaction via nonan-3-one, a simple and efficient production can be achieved.

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Claims (5)

[Claims] 1. The general formula (Ia) [Chemical 1] (In the formula, R¹Is an alkyl group, phenyl group, naphthyl group or
Is a heteroaromatic group, R ³Is a halogen atom, hydroxy
Group, alkoxyl group, acyl group, alkylmercapto
Represents a group or an alkylamino group. ) Has a structure represented by
And at least one site of the asymmetric carbon represented by *
Optically active adaman, characterized in that the compound has optical activity
Tan derivative. 2. The general formula (Ib) [Chemical 2] (In the formula, R¹Is an alkyl group, phenyl group, naphthyl group or
Is a heteroaromatic group, R ²Is an alkyl group, R³Is a halogen
Atom, hydroxyl group, alkoxyl group, acyl group,
An alkylmercapto group or an alkylamino group is shown. )
An optically active adder having a structure represented by
Mantan derivative. 3. A compound represented by the general formula (Ic): (In the formula, R ³ represents a halogen atom, a hydroxyl group, an alkoxyl group, an acyl group, an alkylmercapto group or an alkylamino group, and R ⁴ and R ⁵ each represent an alkyl group, which may be the same or different. Good.)
An optically active adamantane derivative having a structure represented by: 4. A method for producing an optically active adamantane derivative, which comprises passing through 7-methylenebicyclo [3.3.1] nonan-3-one. 5. The method for producing an optically active adamantane derivative according to claim 1, 2 or 3, which is via 7-methylenebicyclo [3.3.1] nonan-3-one.