JP2896582B2 - Optically active alcohol having a silyl group at the γ-position and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel optical activity having a stereoregularity having a silyl group at the γ-position, which is useful as an intermediate for pharmaceuticals and agricultural chemicals, for example, a synthetic intermediate for prostaglandins. The present invention relates to alcohol and a method for producing the same.

2. Description of the Related Art Tertiary allyl alcohol is a useful compound per se, and has been widely recognized as a useful synthetic intermediate. In particular, in recent years, various physiologically active compounds having a tertiary allyl alcohol skeleton in the molecular structure have become widely known. However, these compounds are mostly optically active substances, and optically active Synthesis of the body is an important industrial issue.

In particular, the final target compound--many of which contains an optically active allylic alcohol skeleton in its molecular structure, and considering the synthesis of more complex compounds and their stereoisomeric prostaglandins, these As an intermediate that can be advantageously synthesized, a tertiary allyl alcohol having optical activity that enables various reaction operations to be performed extremely easily is desired. For example, the following formula [VI] which is a synthetic prostaglandin containing a tertiary optically active allyl alcohol skeleton in the ω chain portion: Albaprostil has anti-ulcer activity and is expected to be used in medicine, but as a synthetic intermediate of this formula (VI), the following formula (VII) An inexpensive method for synthesizing an optically active tertiary allyl alcohol represented by the following formula is desired.

Conventionally, as a method for synthesizing optically active allyl alcohol, the following formula [VIII] (Where R and R ′ are an alkyl group or a phenyl group, respectively), or an asymmetric reduction method of a conjugated enone represented by the following formula [IX]: (Where R ″ is an alkyl group or a phenyl group, and A is a silyl group or a stannyl group.) A method by kinetic optical resolution by asymmetric epoxidation of allyl alcohol (JP-A-63-225384, Id 64
Publication No. -6266) has been proposed.

However, these methods are methods for synthesizing optically active forms of secondary allylic alcohols and cannot be directly applied to synthesis of optically active forms of tertiary allyl alcohol.

In order to obtain an optically active tertiary allyl alcohol, there are not many known synthesis methods as compared with the secondary allylic alcohol, but the separation is carried out mainly with phthalic anhydride using an amine-based resolving agent. The method has been done. However, this method has many problems, such as the need for inclusions, unpredictability of compatibility with the resolving agent, and the need for expensive resolving agents.

Further, as a method for synthesizing an optically active tertiary allyl alcohol, the following formula After optically resolving the tertiary inol in the same manner as described above, there is a method in which an addition reaction is performed on the triple bond portion. However, this method has the same problem as the former in terms of resolution, and has the disadvantage that a mixture of cis and trans is generated in the addition reaction.

Further, there is also known an example in which a cerami compound is synthesized as shown in the following reaction formula to synthesize a prostaglandin analog (JSS Kotnicke et al., J. Med. Chem., 20, p1551, 1977).

However, the produced prostaglandin analog is a cerami mixture, and it has been difficult to obtain a single optically active compound.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a tertiary allyl alcohol having an optical activity useful as an intermediate for pharmaceuticals, agricultural chemicals, and the like, and an inexpensive and efficient production method thereof. Aim.

Means and Action for Solving the Problems The present inventor has conducted intensive studies to achieve the above object, and as a result, the following general formula [III] Or the following general formula (IV) (Wherein, R ¹ , R ² , and R ³ are the same or different alkyl groups having 1 to 10 carbon atoms, and R ⁴ is an alkyl group having 1 to 10 carbon atoms, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl Group, hexa-4-yn-2-yl group,
Hepta-4-yn-2-yl group, 2,6-dimethyl-hepta-5-en-1-yl group, penta-1-en-1-yl group, penta-2-en-1-yl group, Hex-1-en-2-yl group, 3-ethoxy-2-methyl-propan-2-yl group, ethoxyethyl group, 5-methoxyhexyl group, 6-methoxy-2-hexyl group, methyl halide group, N-butyl halide, n-pentyl halide, nonyl halide, phenyl, benzyl,
Halogenated phenyl group, n-pentyloxymethyl group,
1-ethoxy-2-methyl-propan-2-yl group, phenoxymethyl group, benzyloxymethyl group, p-chloro-phenoxymethyl group, 2-phenylethyl group, benzyloxyethyl group, phenylacetylenyl group, m -Chloro-phenoxymethyl group, m-trifluoromethyl-phenoxymethyl group, 1-butyl-cyclopropyl group, 3-
It is a group selected from an ethyl-cyclopentyl group, a 2-octenyl group and a vinyl group. An epoxy ketone compound having a silyl group at the γ-position represented by the following general formula [V] R ⁵ MgX [V] (where R ⁵ is an alkyl group having 1 to 10 carbon atoms different from R ⁴ , Cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, hexa-4-yn-2-yl group,
Hepta-4-yn-2-yl group, 2,6-dimethyl-hepta-5-en-1-yl group, penta-1-en-1-yl group, penta-2-en-1-yl group, Hex-1-en-2-yl group, 3-ethoxy-2-methyl-propan-2-yl group, ethoxyethyl group, 5-methoxyhexyl group, 6-methoxy-2-hexyl group, methyl halide group, N-butyl halide, n-pentyl halide, nonyl halide, phenyl, benzyl,
Halogenated phenyl group, n-pentyloxymethyl group,
1-ethoxy-2-methyl-propan-2-yl group, phenoxymethyl group, benzyloxymethyl group, p-chloro-phenoxymethyl group, 2-phenylethyl group, benzyloxyethyl group, phenylacetylenyl group, m -Chloro-phenoxymethyl group, m-trifluoromethyl-phenoxymethyl group, 1-butyl-cyclopropyl group, 3-
X is a group selected from an ethyl-cyclopentyl group, a 2-octenyl group and a vinyl group, and X is a chlorine atom, a bromine atom or an iodine atom. After reacting the organomagnesium reagent represented by the formula (1), hydrolysis is carried out, so that an expensive resolving agent is not required, and the stereostructure of the obtained optically active tertiary allyl alcohol is predicted. Formula [I] Or the following general formula (II) (Wherein, R ¹ , R ² , and R ³ are the same or different alkyl groups having 1 to 10 carbon atoms, and R ⁴ and R ⁵ are different alkyl groups having 1 to 10 carbon atoms, cyclopentyl group) , Cyclohexyl group, cyclohexylmethyl group, hexa-4-
An in-2-yl group, a hepta-4-in-2-yl group, 2,
6-dimethyl-hepta-5-en-1-yl group, penta-1-en-1-yl group, penta-2-en-1-yl group, hexa-1-en-2-yl group, 3- Ethoxy-2
-Methyl-propan-2-yl group, ethoxyethyl group,
5-methoxyhexyl group, 6-methoxy-2-hexyl group, methyl halide group, n-butyl halide group, n-pentyl halide group, nonyl halide group, phenyl group, benzyl group, phenyl halide group, n-pentyloxymethyl group, 1-ethoxy-2-methyl-propan-2-yl group, phenoxymethyl group, benzyloxymethyl group, p-chloro-phenoxymethyl group, 2-phenylethyl group, benzyloxyethyl group, Phenylacetylenyl group, m-chloro-phenoxymethyl group, m-trifluoromethyl-phenoxymethyl group, 1-butyl-cyclopropyl group, 3-ethyl-cyclopentyl group, 2-octenyl group, vinyl group It is. ), An optically active alcohol having a silyl group at the γ-position can be synthesized, and this optically active alcohol can perform various reaction operations extremely easily,
The present inventors have found that they are useful as intermediates for agricultural chemicals, for example, synthetic intermediates for prostaglandins, and have accomplished the present invention.

Accordingly, the present invention provides an optically active alcohol having a silyl group at the γ position selected from the compounds represented by the formulas (I) and (II), and a silyl group at the γ position represented by the formula (III) or (IV). After reacting an epoxyketone compound having a group with an organomagnesium reagent represented by the above formula [V], hydrolysis is performed.
The present invention provides a method for producing an optically active alcohol having a silyl group at the 2-position.

 Hereinafter, the present invention will be described in more detail.

The following general formulas [I] and [II] of the present invention In the optically active alcohol having a silyl group at the γ-position represented by the formula, all of the substituents R ¹ , R ² and R ³ are alkyl groups having 1 to 10 carbon atoms, specifically
-Propyl group, i-propyl group, n-butyl group, i-butyl, t-butyl group, acyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. Note that R ¹ , R ² , and R ³ may be the same or different groups.

Further, specific examples of the substituents R ⁴ and R ⁵ having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, i-butyl 1, t-butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, 2-methylhexyl group,
Examples thereof include a methyl-2-hexyl group and a 2-hexyl group. R ⁴ and R ⁵ are groups that are not the same as each other.

The optically active alcohol having a silyl group at the γ-position in the above formulas [I] and [II] of the present invention is represented by the following general formula [III] Or the following general formula (IV) (Wherein R ¹ , R ² , R ³ , and R ⁴ are the same as described above) and an epoxyketone compound having a silyl group at the γ-position represented by the following general formula [V] R ⁵ MgX ... [V (Wherein, R ⁵ and X are the same as those described above). Here, the above [III],
[IV] The epoxy ketone compound having a silyl group at the γ-position of the formula can be obtained, for example, by the method described in JP-A-63-225384.

That is, as shown in the following reaction formula, [III],
[IV] An epoxy ketone compound having a silyl group at the γ-position of the formula is obtained.

Examples of the organomagnesium reagent of the formula [V] include, for example, CH ₃ MgI, C ₂ H ₅ MgBr, n—C ₄ H ₉ MgBr, And the like. The amount of organomagnesium reagent added is
The amount is preferably 0.5 to 4 equivalents, more preferably 0.8 to 1.5 equivalents to the epoxy ketone compound having a silyl group at the γ-position in the formulas [III] and [IV].

In this case, the reaction of the epoxy ketone compound having a silyl group at the γ-position of the formulas [III] and [IV] with the organomagnesium reagent of the formula [V] is preferably carried out in an organic solvent. Typically, tetrahydrofuran,
Ethers such as dioxane, dimethoxyethane and diethyl ether, hydrocarbons such as hexane and pentane, and polar solvents such as dimethylformamide (DMF), hexamethylphosphoramide (HMPA) and dimethylsulfoxide (DMSO) are used. , A single or mixed solvent thereof can be used. Particularly, the organic solvent is preferably used after removing water as much as possible in view of the nature of the reaction, and tetrahydrofuran or a solvent obtained by adding HMPA thereto is more preferably used.

Further, this reaction is desirably performed in an inert atmosphere such as argon or nitrogen, and the reaction conditions are not particularly limited, but may be -100 to 30 ° C, particularly -78 to 0 ° C, for 10 minutes to 15 hours, particularly Preferably, it is 0.5 to 5 hours.

The selectivity to the carbonyl surface of the present reaction usually varies depending on conditions such as the combination of the substituents R ⁴ and R ⁵ , the type of the solvent, and the reaction temperature, but when the organomagnesium reagent of the formula (V) is used, , [III] and [IV] from the epoxy ketone compounds having a silyl group at the γ-position, respectively [I],
[II] An optically active alcohol having a silyl group at the γ-position of the formula is mainly produced, and gives almost a single stereoisomer. When a stereoisomer is by-produced in this reaction, it is preferable to purify the product by column chromatography or the like, if necessary.

Although the hydrolysis reaction conditions of the present invention are not particularly limited, for example, treatment with a saturated aqueous solution of ammonium chloride or the like can be mentioned.

[I] and [II] according to the present invention thus obtained.
The optically active alcohol having a silyl group at the γ-position of the formula can be converted to an optically active allyl alcohol or an optical antipode of γ-tin substitution by reacting with an organotin lithium reagent as shown in the following reaction formula, for example. When further reacted with iodine, an optically active allyl alcohol substituted with γ-iodine or an optical antipode thereof can be obtained.

(However, in the formula, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same as described above.)
R ⁶ , R ⁷ and R ⁸ are the same or different alkyl groups having 1 to 10 carbon atoms. In this case, when reacting the compounds [I] and [II] with the organotin lithium reagent, as the organotin lithium reagent, for example, tri-n-butyltin lithium, triethyltin lithium or the like is used. The reagent is preferably used in an amount of 0.5 to 4 equivalents, particularly 0.8 to 2.2 equivalents, based on the compounds [I] and [II].

Further, the reaction is desirably carried out using a solvent, and the solvent used for the reaction may be any one which does not inhibit the reaction, for example, tetrahydrofuran, hexane, pentane,
Diethyl ether and the like.

The reaction temperature is usually from -100 ° C to the boiling point of the solvent, preferably from -40 to 40 ° C, and the reaction time is usually from 5 minutes to 50 hours.

Further, when reacting the iodine with the γ-tin-substituted optically active allyl alcohol [XII] or [XIV] obtained by the above reaction, iodine is added to the compound [XI] or [XIV] in an amount of 0.5%.
It is preferable to use 3 to 3 equivalents, particularly 0.8 to 1.6 equivalents.

This reaction is desirably performed using a solvent that does not inhibit the reaction, and it is preferable to use, for example, diethyl ether, hexane, pentane, or the like as the solvent.

Furthermore, when an aqueous solution of sodium hydrogencarbonate coexists in this reaction, reaction impurities can be reduced. Addition of an aqueous solution of sodium hydrogencarbonate is carried out using compounds [XI], [XIV]
It is preferable that the amount is an excess of 1 equivalent or more.

The reaction temperature is usually -20 to 40C, preferably -5 to
The reaction time is usually 5 to 20 hours.

Then, the obtained γ-tin-substituted optically active allyl alcohol, γ-iodine-substituted optically active allyl alcohol and their optical enantiomers are silyl-protected according to the following reaction formula, and then subjected to a method such as Skotnicki et al. Med.Chem., 20, p1551,
1977) and the method proposed by the present inventors in Japanese Patent Application No. 63-57019 can be used to synthesize optically active prostaglandins.

[Effects of the Invention] The optically active alcohol having a silyl group at the γ-position of the present invention is useful as an intermediate for pharmaceuticals and agricultural chemicals, for example, a synthetic intermediate for prostaglandins.

Further, according to the production method of the present invention, an expensive resolving agent is not required, and the stereostructure of the obtained optically active alcohol having a silyl group at the γ-position can be predicted, and the compound can be efficiently synthesized at low cost. .

<Examples> Hereinafter, the present invention will be described in detail with reference to Examples and Reference Examples, but the present invention is not limited to these Examples. In the following formula, Me is a methyl group, Et is an ethyl group, n-Bu is an n-butyl group, n-Am is an n-amyl group,
Ph represents a phenyl group.

[Reference Example 1] Oxalic acid chloride (2.41 ml, 27.6 mmol) was added to methylene chloride (46 ml) cooled at −60 ° C. under an argon atmosphere. At −60 ° C., dimethyl sulfoxide (3.91 ml, 55.1 mm
ol) was added dropwise, followed by stirring for 10 minutes. Epoxy alcohol (7) (3.97 g, 18.4 mmol) in methylene chloride (20 m
l) was added and the mixture was stirred at −60 ° C. for 20 minutes, and then triethylamine (15.3 ml, 110.3 mmol) was added dropwise. After stirring the reaction mixture at -60 ° C for 30 minutes, the temperature was raised to room temperature over 1 hour. After adding a saturated saline solution (60 ml) and stirring, hexane (60 ml) was added. The organic layer is separated, and saturated saline (60 m
l) followed by washing with saturated aqueous NaHCO ₃ (60 ml).
The aqueous layer was extracted with hexane (60 ml), and the obtained organic layer was extracted with Mg.
And dried over SO _4. After that, the solvent of the liquid was distilled off under reduced pressure to obtain about 4 g of a crude product. By purifying by silica gel column chromatography, epoxy ketone (2) (3.66 g) was obtained with a yield of 93%. The characteristic values of the epoxy ketone (2) were as follows. ¹ H NMR (CCl ₄ , PhH): δ 0.22 (s, 9 H), 0.92 (t, J = 6.0 H
z, 3H), 1.15-1.90 (m, 6H), 2.10-2.45 (m, 3H), 3.09
(D, J = 3.7 Hz, 1H) IR (neat): 2930, 1705, 1250, 843 cm ^-1 Rf = 0.55 (hexane: ether = 5: 1) [Example 1] Under argon atmosphere, THF (65.7ml), HMPA (21.9m
l), methylmagnesium iodide (6.69 ml, 2.55N in ether, 17.1 mmol) were mixed at room temperature. This is -78
And cooled to 2.degree. C., epoxy ketone (2) (2.81 g, 13.13 mmo)
A solution of l) in THF (10 ml) was slowly added dropwise. The temperature was raised to 0 ° C. over about 2 hours, and a saturated aqueous NH ₄ Cl solution (100 ml) was added. Extract with hexane (100 ml) and separate the resulting organic layer with MgS
And dried over O _4. After that, the solvent of the liquid was distilled off under reduced pressure.
The obtained crude product (2.86 g) was purified by silica gel column chromatography, whereby epoxy alcohol (3) (2.67 g) was obtained with a yield of 89%. The characteristic values of the epoxy alcohol (3) are as follows. When ¹ H NMR and ¹³ C NMR were analyzed, anti: syn was> 9.
9: <1. ¹ H NMR (CCl ₄ , PhH): δ 0.21 (s, 9 H), 0.99 (t, J = 6.0 H
z, 3H), 1.20-1.80 (m, 8H), 1.31 (s, 3H), 1.94, (brs,
1H), 2.33 (d, J = 3.8 Hz, 1H), 2.63 (d, J = 3.8 Hz, 1H) ¹³ C NMR (CDCl ₃ ): δ 69.4, 61.7, 48.1, 39.0, 32.4, 26.5,
23.0, 22.5, 13.9, -3.7 Rf = 0.25 (hexane: ether = 4: 1) IR (neat): 3470, 2960, 1460, 1250, 840 cm ^-1 ▲ [α] ²⁵ _D ▼: +13.6 (c3. 18, CHCl ₃ ) (EX-1079) [Reference Example 2] Under argon atmosphere, diisopropylamine (3.61mmo
l, 25.7 ml) in THF (50 ml) at 0 ° C. with n-BuLi (9.
19 ml of a 2.10 N hexane solution, 19.3 mmol) was added thereto, followed by stirring for 30 minutes. Then, at 0 ° C., epoxy alcohol (3)
(1.48 g, 6.43 mmol) and a solution of THF (8 ml) were added. After stirring for 3 hours, n-Bu ₃ SnH (2.59 ml, 9.65 mmol) was added at 0 ° C., followed by heating to room temperature and stirring for 3 hours. Saturated saline (80m
l) and hexane (50 ml) were added. After liquid separation, the organic layer was dried over MgSO ₄
And dried. After that, the liquid was distilled off under reduced pressure to obtain 3.71 g of a crude product of (4). The obtained crude product was directly used for the next reaction.

The characteristic values of compound (4) were as follows. ¹ H NMR (CONHz, CCl ₄ , N ₄ Si): δ 0.40 (m, 29H), 1.14
(S, 3H), 5.88 (s, with.satellite ccupling (J = 75.6)
Hz, and 79.2 Hz, 2H) ¹³ C NMR (90 MHz, CDCl ₃ ): δ155.0,122.7, satellite, 1
6.4ppm, 17.1ppm,), 74.3,42.3,32.2,28.9, satellite, 0.
9ppm, 27.7,27.0, (satellite, 2.3ppm), 23.6,22.5,13.8,13.4,9.3 (satellite, 14.5ppm, 15.2pp
m). IR (neat): 3380, 2900, 1600, 1450, 940 cm ^-1 ▲ [α] ²⁵ _D ▼: + 4.2 ° (c2.56, CHCl ₃ ) (EX-1100) [Reference Example 3] The crude product of (4) (3.71 g) obtained in the previous reaction was dissolved in ether (30 ml). Saturated NaHCO ₃ aqueous solution (30ml)
After cooling to 0 ° C., iodine (1.9 g, 7.49 mmol) was added little by little over 15 minutes while stirring well. 0
After stirring at 20 ° C. for 20 minutes, a saturated aqueous solution of Na ₂ S ₂ O ₄ (50 ml) was added and the mixture was stirred. When the iodine color disappeared, the layers were separated and the organic layer was washed with 3N aqueous NaOH (30 ml) followed by water (30 ml). The aqueous layer was extracted with ether (50ml) and 3N NaOH (20m
l), washed with water (20 ml). The obtained organic layer was dried over MaSO ₄ and passed, and the solvent of the liquid was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography, and compound (5) (1.56 g) was obtained in two steps at a yield of 90%.
%. The characteristic values of compound (5) were as follows. ¹ H NMR (CCl ₄ , Me ₄ Si): δ 0.85 (t, J = 6.0 Hz, 3H), 1.0
5-1.90 (m, 8H), 1.20 (s, 3H), 2.48, (brs, 1H), 6.15
(D, J = 15.6Hz, 1H), 6.41 (d, J = 15.6Hz, 1H) [Reference Example 4] To a solution of iodoalcohol (5) (1.40 g, 5.23 mmol) in DMF (10 ml) at 0 ° C. was added imidazole (0.71 g, 10.5 g).
mmol) and triethylsilyl chloride (1.05 ml, 6.28 mm)
ol), and the mixture was heated to room temperature and stirred for 5 hours. Hexane (50 ml) and a saturated aqueous solution of NaHCO ₃ (50 ml) were added, and the mixture was stirred and then separated. After drying the obtained organic layer with MgSO ₄ ,
Then, the solvent of the liquid was distilled off under reduced pressure. When the obtained crude product (2.38 g) was purified by silica gel column chromatography, compound (6) (1.82 g) was obtained in a yield of 91.
%. The characteristic values of compound (6) are as follows. ¹ H NMR (CCl ₄ , PhH): δ 0.66 (t, J = 6.6 Hz, 6 H), 0.80 −
1.90 (m, 2H), 1.32 (s, 3H), 6.16 (d, J = 15.4Hz, 1H),
6.47 (d, J = 15.4 Hz, 1H) ¹³ C NMR (CDCl ₃ ): δ 153.1, 78.2, 74.7, 43.5, 32.2, 27.
2,23.5,22.6,14.0,6.9,6.5 ▲ [α] ²⁵ _D ▼: + 21.6 ° (c3.01, CHCl ₃ ) Rf = 0.70 (hexane) Examples 2 to 9 Epoxy shown in Table 1 When a reaction was carried out in the same manner as in Example 1 using a ketone compound and an organomagnesium reagent,
An optically active alcohol having a silyl group at the γ-position shown in Table 1 was obtained.

The characteristic values of the epoxy ketone compounds obtained in Examples 3 to 7 are as follows.

Epoxy ketone compound of Example 3 ¹³ C NMR (200 MHz, CDCl ₃ ): δ 70.8, 60.3, 46.7, 39.3, 29.
3,25,2,23.0,13.7,7.3, −4.1 ¹ H NMR (200 MHz, CDCl ₃ ): δ0.04 (s, 9H), 0.77-1.03
(M, 6H), 1.18-1.68 (m, 8H), 1.83 (brs, 1H), 2.33
(D, J = 3.8 Hz, 1 H), 2.74 (d, J = 3.8 Hz, 1 H) IR (neat): 3450, 2920, 2860, 1250, 860, 830 cm ^-1 Epoxy ketone compound of Examples 4 and 5 ¹³ C NMR (200 MHz, CDCl ₃ ): δ 69.1, 61.5, 47.6, 38.4, 26.
1,25,2,22.9,13.6, −5.0 ¹ H NMR (200 MHz, CDCl ₃ ): δ0.04 (s, 9H), 0.87 (t, J =
7.0Hz, 3H), 1.12-1.57 (m, 6H), 1.26 (s, 3H) 1.81 (br
s, 1H) 2.38 (d, J = 3.7 Hz, 1H), 2.72 (d, J = 3.7 Hz, 1H) IR (neat): 3400, 2940, 1250, 1060, 840 cm ^-1 Epoxy ketone compound of Example 6 ¹³ C NMR (200 MHz, CDCl ₃ ): δ 70.9, 60.3, 46.7, 36.0, 32.
5,25,3,23.1,13.8,7.4, −4.0 ¹ H NMR (200 MHz, CDCl ₃ ): δ0.02 (s, 9H), 0.84 (t, J =
6.5Hz, 3H), 0.90 (t, J = 7.6Hz, 3H), 1.15-1.50 (m, 6
H), 1.57 (q, J = 7.6 Hz, 2H), 1.86 (brs, 1H) 2.30 (d, J
= 3.7Hz, 1H), 2.72 (d, J = 3.7Hz, 1H) IR (neat): 3480,2920,1240,830cm ^-1 Epoxy ketone compound of Example 7 ¹³ C NMR (200 MHz, CDCl ₃ ): δ 145.1, 128.2, 127.0, 125.
3,73.6,61.7,48.4,38.5,25.1,22.8,13.7, −4.0 ¹ H NMR (90 MHz, CCl ₄ , PhH): δ0.29 (s, 9H), 0.80-2.0
8 (m, 9H), 2.31 (brs, 1H), 2.47 (d, J = 3.6Hz, 1H), 3.2
0 (d, J = 3.6 Hz, 1H), 7.10-7.60 (m, 5H)

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-225384 (JP, A) Am. Chem, Soc. , 110 [9] (1988), 2978-2979 Tetrahedron, 44 [13] (1988), 4073-4086 (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/08 C07F 7/22 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula [I] And the following general formula [II] (Wherein, R ¹ , R ² and R ³ are the same or different alkyl groups having 1 to 10 carbon atoms, and R ⁴ and R ⁵ are different alkyl groups having 1 to 10 carbon atoms and cyclopentyl group, respectively) , Cyclohexyl group, cyclohexylmethyl group, hexa-4-
An in-2-yl group, a hepta-4-in-2-yl group, 2,
6-dimethyl-hepta-5-en-1-yl group, penta-1-en-1-yl group, penta-2-en-1-yl group, hexa-1-en-2-yl group, 3- Ethoxy-2
-Methyl-propan-2-yl group, ethoxyethyl group,
5-methoxyhexyl group, 6-methoxy-2-hexyl group, methyl halide group, n-butyl halide group, n-pentyl halide group, nonyl halide group, phenyl group, benzyl group, phenyl halide group, n-pentyloxymethyl group, 1-ethoxy-2-methyl-propan-2-yl group, phenoxymethyl group, benzyloxymethyl group, p-chloro-phenoxymethyl group, 2-phenylethyl group, benzyloxyethyl group, Phenylacetylenyl group, m-chloro-phenoxymethyl group, m-trifluoromethyl-phenoxymethyl group, 1-butyl-cyclopropyl group, 3-ethyl-cyclopentyl group, 2-octenyl group, vinyl group It is. An optically active alcohol having a silyl group at the γ-position selected from the compounds represented by the formula: 2. The following general formula [III] Or the following general formula [IV] (Wherein, R ¹ , R ² , and R ³ are the same or different alkyl groups having 1 to 10 carbon atoms, and R ⁴ is an alkyl group having 1 to 10 carbon atoms, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl Group, hexa-4-yn-2-yl group,
Hepta-4-yn-2-yl group, 2,6-dimethyl-hepta-5-en-1-yl group, penta-1-en-1-yl group, penta-2-en-1-yl group, Hex-1-en-2-yl group, 3-ethoxy-2-methyl-propan-2-yl group, ethoxyethyl group, 5-methoxyhexyl group, 6-methoxy-2-hexyl group, methyl halide group, N-butyl halide, n-pentyl halide, nonyl halide, phenyl, benzyl,
Halogenated phenyl group, n-pentyloxymethyl group,
1-ethoxy-2-methyl-propan-2-yl group, phenoxymethyl group, benzyloxymethyl group, p-chloro-phenoxymethyl group, 2-phenylethyl group, benzyloxyethyl group, phenylacetylenyl group, m -Chloro-phenoxymethyl group, m-trifluoromethyl-phenoxymethyl group, 1-butyl-cyclopropyl group, 3-
It is a group selected from an ethyl-cyclopentyl group, a 2-octenyl group and a vinyl group. And an epoxy ketone compound having a silyl group at the γ-position represented by the following general formula [V] R ⁵ MgX [V] (where R ⁵ is an alkyl group having 1 to 10 carbon atoms different from R ⁴ , Cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, hexa-4-yn-2-yl group, hepta-4-yn-2-yl group, 2,6-dimethyl-hepta-5-en-1-yl group, penta -1-en-1-yl group, penta-2-en-1-yl group, hexa-1-en-2-yl group, 3-ethoxy-2-methyl-propane-
2-yl group, ethoxyethyl group, 5-methoxyhexyl group, 6-methoxy-2-hexyl group, methyl halide group, n-butyl halide group, n-pentyl halide group, nonyl halide group, phenyl group Benzyl, halogenated phenyl, n-pentyloxymethyl, 1
-Ethoxy-2-methyl-propan-2-yl group, phenoxymethyl group, benzyloxymethyl group, p-chloro-
Phenoxymethyl group, 2-phenylethyl group, benzyloxyethyl group, phenylacetylenyl group, m-chloro-
A group selected from a phenoxymethyl group, an m-trifluoromethyl-phenoxymethyl group, a 1-butyl-cyclopropyl group, a 3-ethyl-cyclopentyl group, a 2-octenyl group and a vinyl group, and X is a chlorine atom or a bromine atom Or an iodine atom. ) Is reacted and then hydrolyzed.) The following general formula [I] Or the following general formula [II] (However, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ in the formula are the same as described above.) A method for producing an optically active alcohol having a silyl group at the γ-position shown in the formula: