JPH08217775A - New crown thioether and its transition metallic complex and production of optically active alcohol using the same - Google Patents

Abstract

PURPOSE: To obtain the subject new compound which is a crown thioether, having a specific structure, acting as a ligand of a catalyst for asymmetric synthesis and capable of providing complexes with various transition metals enabling the asymmetric synthesis of a high reactional selectivity, conversion rate, catalyst activity and optical purity. CONSTITUTION: This new crown thioether is represented by formula I. The compound is useful as a ligand, etc., of a catalyst for asymmetric synthesis and capable of forming a complex with a transition metal such as Co, Ni, Ru, Rh, Pd, Ir, Cr, Mo, Mn, Hg, Cu, Ag, Au, Pt or Tc and manifesting excellent performances of the complex in reactional selectivity, conversion rate, catalyst activity, optical purity, etc., in asymmetric synthesis such as asymmetric alkylation, silylation, formylation, etc. The compound is obtained by reacting (R)-(+)-1,1'-binaphthalene-2,2'-dithiol of formula III derived from 2,2'-binaphthol of formula II with 3-bromo-2,2-dimethyl-1-propanol, providing a compound of formula IV, methanesulfonylating the resultant compound of formula IV and subsequently reacting the prepared compound of formula IV with a dithiol of formula III.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel crown thioether compound and a transition metal complex thereof, and more specifically, a crown thioether compound useful as a catalyst for various asymmetric synthesis reactions and a transition having the same as a ligand. The present invention relates to a metal complex and a method for producing an optically active alcohol using the optically active complex.

[0002]

2. Description of the Related Art Conventionally, many transition metal complexes have been used as catalysts for organic synthesis reactions, and in particular, noble metal complexes are stable and easy to handle, so they are used as catalysts even though they are expensive. Many synthetic studies have been carried out, and many reports have been made that have enabled organic synthetic reactions that were impossible by conventional means.

In recent years, crown thioether-transition metal complexes using a transition metal such as nickel, cobalt, copper, ruthenium, rhodium, and silver with a crown thioether as a ligand have been synthesized (Stephen R. Coop.
er, Acc. Chem. Res. 1988, 21, 141)), and cannot be used as a catalyst for asymmetric synthesis reaction because its ligand is not an optically active substance. Further, regarding optically active crown thioethers, RM Kellogg (Kellog
g) et al. (J. Chem. Soc., Chem. Commun. 1984, 309
Page; Tetrahedron Lett. 1985, 29, 3499), but the metal complexes thereof have not yet been isolated.

[0004]

As described above, as a catalyst for an asymmetric synthesis reaction, a crown thioether-transition metal complex excellent in substrate selectivity, reaction conversion rate, catalytic activity, optical purity and the like is used. Isolation is desired, but none of them has been obtained yet.

Therefore, there has been a demand for the provision of new crown thioether compounds which are novel and give complexes having excellent catalytic ability in asymmetric synthesis reactions. There has also been a demand for development of a novel catalytic asymmetric reaction utilizing the above crown thioether-transition metal complex as a catalyst. The present invention aims to satisfy these demands.

[0006]

Means for Solving the Problems The present inventors have conducted diligent research on a complex having an excellent catalytic ability in an asymmetric synthesis reaction. As a result, the atropisomeric 2,2'-vitrilyl skeleton was found to be unsuccessful. A transition metal complex having an optically active crown thioether as a chiral source as a ligand was isolated and obtained, and a patent application was filed (Japanese Patent Application No. 6-301471).

[0007] Further, as a result of continuing diligent research,
A transition metal complex having an optically active crown thioether having an atropisomeric 1,1'-binaphthyl skeleton as an asymmetric source represented by the following formula (1) as a ligand is newly isolated and obtained. The inventors have found that they are excellent in terms of substrate selectivity, reaction conversion rate, catalytic activity, optical purity, etc. in the simultaneous synthesis reaction, and have completed the present invention.

Therefore, the object of the present invention is to provide the following general formula (1):

Embedded image The present invention provides a crown thioether compound represented by Further, another object of the present invention is to provide a transition metal-crown thioether complex having this crown thioether compound as a ligand. Still another object of the present invention is to provide a method for producing an optically active alcohol using the above transition metal-crown thioether complex.

The binaphthyl skeleton of the crown thioether compound (1) of the present invention has an optically active form and a racemic form,
Although a meso form exists, the present invention includes any of these optical isomer compounds.

The crown thioether compound (1) of the present invention is produced, for example, by the method represented by the following reaction formula.

Embedded image (In the formula, Me represents a methyl group, Et represents an ethyl group, and Ms represents a methanesulfonyl group.)

That is, first, D. Fabbri
(J. Org. Chem. 1993, 58, 1748), anionization of 2,2′-binaphthol (2) with sodium hydride in dimethylformamide (DMF), to which dimethylthiocarbamoyl chloride was added. Is added and reacted.

Then, the obtained 1,1'-binaphthalene-
2,2′-diyl-O, O-bis (N, N-dimethylthiocarbamate) (3) is heated without solvent to transfer it,
It is designated as 1,1′-binaphthalene-2,2′-diyl-S, S-bis (N, N-dimethylthiocarbamate) (4).
The obtained compound (4) is tetrahydrofuran (THF)
Medium, reduction with lithium aluminum hydride gives 1,1′-binaphthalene-2,2′-dithiol (5).

Further, to this compound (5), sodium ethoxide was used as a base and 3-bromo-2,2'-dimethyl-1-propanol was added, and 2,2'-bis (2,2-) was added.
This leads to dimethyl-3-hydroxypropylthio) -1,1'-binaphthalene (6).

Finally, the hydroxyl group of this compound (6) is mesylated to give 2,2'-bis (2,2-dimethyl-3-methanesulfonylpropiothio) -1,1'-binaphthalene (7), The crown thioether compound (1) of the present invention is produced by adding cesium carbonate in DMF and another molecule of compound (5).

To obtain a transition metal-crown thioether complex from the crown thioether compound (1) of the present invention obtained as described above, for example, "Chemical Review (Chem. Rev.)", Vol. 81, p. 365. (1981
The method can be produced by a known method such as the method described in (1) or a method similar thereto.

For example, Ni (ClO ₄ ) ₂ .6H ₂ O, Cu
_{(ClO 4) 2, Hg (} ClO 4) 2 · 3H 2 O, [Pd (C
H ₃ CN) _4] (BF _{4) 2,} [RhCl (COD) _{2] 2,}
[Co (CH ₃ CN) ₆ ] (BF ₄ ) ₂ , PtCl ₂ (CO
It can be easily obtained by reacting a transition metal compound such as D) with the crown thioether compound (1).

The transition metals used in the transition metal-crown thioether complex include iron, cobalt, nickel,
Ruthenium, rhodium, palladium, iridium, chromium, molybdenum, manganese, mercury, copper, silver, gold, platinum,
Technicium and the like can be mentioned.

Next, the transition metal-crown thioether complex obtained by the present invention will be exemplified. In addition, L shows the crown thioether compound of Formula (1). Ni (L) Ni (L) Cl ₂ [Ni (L)] (BF ₄ ) ₂ [Ni (L)] (ClO ₄ ) ₂ [Ni (L)] (PF ₆ ) ₂

Pd (L) Cl ₂ Pt (L) Cl Rh (L) Cl [RhCl ₂ (L)] Cl [Rh (L)] ClO ₄ [Rh (L)] PF ₆ [Rh (L)] BF ₄ Ir (L) Cl [Ir (L)] ClO ₄ [Ir (L)] PF ₆ [Ir (L)] BF ₄

Ru (L) Cl ₂ [Ru (L)] (ClO ₄ ) ₂ · (solv) ₂ [Ru (L) Cl ₂ ] PF ₆ [Ru (L) Cl ₂ ] BF ₄ Co (L) Cl ₂ [Co (L) Cl ₂ ] BF ₄ [Co (L) Cl ₂ ] ClO ₄ [Co (L) Cl ₂ ] PF ₆ [Co (L)] (BF ₄ ) ₂ [Co (L)] (ClO ₄ ) ₂ [Co (L)] (PF ₆ ) ₂

Fe (L) Cl ₂ [Cu (L)] (BF ₄ ) ₂ [Cu (L)] (ClO ₄ ) ₂ [Cu (L)] (PF ₆ ) ₂ Mo (L) Cl ₂ [Mo (L) Cl ₂ ] BF ₄ [Mo (L) Cl ₂ ] ClO ₄ [Mo (L) Cl ₂ ] PF ₆ [Hg (L)] (BF ₄ ) ₂ [Hg (L)] (ClO ₄ ) ₂ [Hg (L)] (PF ₆ ) ₂

The transition metal-crown thioether complex of the present invention obtained as described above is used for, for example, a catalyst for asymmetric hydrosilylation reaction of ketones and asymmetric synthesis such as asymmetric alkylation and asymmetric formylation. It can be used as a catalyst. That is, either one of the crown thioether compound (1) having an optical rotation of (+) form or that of (−) form is selected, and the transition metal-crown thioether complex having this as a ligand is used as a catalyst. As a result, an asymmetric compound can be synthesized, and the desired product having a desired absolute configuration can be obtained with high optical purity.

Of these, for example, the asymmetric hydrosilylation reaction can be carried out by reacting a ketone with a hydrosilane in an organic solvent such as tetrahydrofuran or dioxane in the presence of the transition metal-crown thioether complex of the present invention. .

The transition metal-crown thioether complex used in this asymmetric hydrosilylation reaction includes the above-mentioned iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, chromium, molybdenum, manganese, mercury, copper, silver, A transition metal complex such as gold, platinum or technitium can be used.

Further, as the reaction materials, ketones,
Acetophenone, propiophenone, isopropyl phenyl ketone, t-butyl phenyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl t-butyl ketone, methyl benzyl ketone and the like, and hydrosilanes include diphenylsilane, phenylmethylsilane, dichloromethylsilane and diethyl. Silane, α-naphthylphenylsilane, triethoxysilane, triethylsilane,
Silylating agents such as trimethylsilane and dimethylphenylsilane are used respectively.

The amounts of ketones and hydrosilanes used in the above reaction are usually 1: 1 to 1: 2 (molar ratio), but can be appropriately adjusted by the addition ratio of the transition metal-crown thioether complex. . The transition metal-crown thioether complex is usually used in an amount of 0.1 to 10 mol% with respect to the ketones, preferably 1 to 5 mo.
1%.

The reaction is usually -50 to +5 under the above conditions.
20 ° C. at a temperature of 0 ° C., preferably −20 to + 20 ° C.
Although the reaction is completed by reacting for 0 hours, it may be appropriately adjusted depending on the amounts of the reactants used.

The silyl compound obtained by this asymmetric hydrosilylation reaction can be further hydrolyzed with an acid such as dilute hydrochloric acid in a water-soluble organic solvent such as methanol or ethanol to obtain an alcohol.

The alcohol obtained by hydrolysis retains the steric configuration of the silyl compound obtained by the asymmetric hydrosilylation reaction as it is. Therefore, by selecting the optical rotation of the crown thioether compound, the desired optically active alcohol can be obtained. Can be selectively obtained.

[0030]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

The apparatus used for measuring the physical properties in each example are as follows. ¹ H-NMR JOEL-GX500 ¹³ C-NMR JOEL-GX500 MASS JOEL JMS-AX500 IR JASCO FT / IR-5300 Optical rotation JASCO DIP-370 Melting point Yanako micro melting apparatus

In the following examples, the crown thioether compound represented by the above formula (1), that is,
2,3; 4,5; 11,12; 13,14-Tetra (1,2-naphtho) -8,8,17,17-tetramethyl-1,6,10,
15-tetrathiacyclooctadeca-2,4,11,13
-Tetraene is designated as Binaph ₂ Me ₄ [18] S ₄ .

Example 1 (1) (R)-(+)-1,1'-binaphthalene-2,2 '
-Diyl-O, O-bis (N, N-dimethylthiocarbamate) synthesis: 50% sodium hydride 10.56g
(220 mmol) is suspended in 200 ml of DMF,
Under ice bath (R) -1,1'-binaphthol 28.63 g (1
00 mmol) is added. 27.19 g (220 mmol) of N, N-dimethylthiocarbamoyl chloride was added to the solution.
And heat to 85 ° C.

After 1 hour, the reaction mixture was cooled to room temperature,
Pour into 800 ml of potassium hydroxide aqueous solution. A colorless solid forms, which is filtered off and washed with water. The obtained solid was recrystallized from methylene chloride-petroleum ether to give the title compound (41.45 g, yield 90%) as colorless crystals. Melting point: 20 to 28 ° C. [α] _D : + 103.5 ° (c = 1.0 THF)

(2) Synthesis of (R)-(+)-1,1'-binaphthalene-2,2'-diyl-S, S-bis (N, N-dimethylthiocarbamate): (R)-( +)-1,1'-
Binaphthalene-2,2'-diyl-O, O-bis (N, N-
Dimethyl thiocarbamate) 5g (10.85mmo
l) is heated at 285 ° C. for 22 minutes. Cool to room temperature,
The resulting yellow solid is dissolved in methylene chloride and purified by silica gel column chromatography to give the title compound 3.
5 g (yield 70%) was obtained. Melting point: 247 to 249 ° C. [α] _D : + 40.6 ° (c = 1.0 THF)

(3) Synthesis of (R)-(+)-1,1'-binaphthalene-2,2'-dithiol: (R)-(+)-
1,1'-Binaphthalene-2,2'-diyl-S, S-bis (N, N-dimethylthiocarbamate) 4.6 g (10
mmol) was dissolved in 40 ml of THF, and 2.27 g (60 mmol) of lithium aluminum hydride was added at 0 ° C. The reaction mixture is heated at reflux for 4 hours and then cooled. The reaction solution is neutralized by adding water and 10% hydrochloric acid. After extraction with ether and evaporation of the solvent, 2.86 g (yield 90%) of the title compound was obtained as a colorless solid. Melting point: 150 to 151 ° C. [α] _D : −85.9 ° (c = 1.0 CHCl ₃ ).

(4) Synthesis of (R) -2,2'-bis (2,2-dimethyl-3-hydroxypropylthio) -1,1'-binaphthalene: In a 300 ml three-necked flask under a nitrogen stream. , Ethanol 60 ml, sodium metal 360
mg (15.7 mmol) is added to prepare an ethanol solution of sodium ethoxide. (R) -1,1'-Binaphthalene-2,2'-dithiol 2.00 g (6.29 m
(mol) is dissolved in 40 ml of ethanol, added with a syringe, and refluxed at 90 ° C. (oil bath) for 30 minutes.

After cooling to room temperature, 2.62 g (15.7 mmo) of 3-bromo-2,2-dimethyl-1-propanol.
l) is added and refluxed at 90 ° C. (oil bath) for 48 hours.
After completion of the reaction, the solvent was distilled off under reduced pressure, water was added to treat the remaining sodium ethoxide, and then the mixture was extracted with chloroform. After drying over anhydrous magnesium sulfate and distilling off chloroform, the residue was purified by silica gel column chromatography (developing solvent: chloroform) to give the title compound as a white solid.
2.59 g (84% yield) was obtained.

The optical purity of the obtained compound was determined by HPLC.
(Product name “CHIRALCEL OD” manufactured by Daicel Chemical Industries, Ltd., mobile phase: 1% isopropanol / hexane solvent). Optical purity> 99% ee.

Melting point: 151 to 152 ° C. [α] _D : + 73.3 ° (c = 1.0 CHCl ₃ ) EI-MS (70 eV): 490 (M ⁺ ).

¹ HNMR (δ, ppm, CDCl ₃ ) 0.78 (s, 6H, CH ₃ ) 0.92 (s, 6H, CH ₃ ) 2.40 (s, 2H, OH) 2.91 (d , J = 11.6, 2H, SCH ₂ ) 3.07 (d, J = 11.6, 2H, SCH ₂ ) 3.10 (d, J = 11.3, 2H, OCH ₂ ).

3.30 (d, J = 11.3, 2H, OCH ₂ ) 6.98 (d, J = 7.8, 2H, ArH) 7.23 (dd, J = 7.8, 7. 8, 2H, ArH) 7.40 (dd, J = 7.8, 7.8, 2H, ArH) 7.69 (d, J = 8.9, 2H, ArH) 7.88 (d, J = 7.8, 2H, ArH) 7.94 (d, J = 8.9, 2H, ArH)

¹³ CNMR (δ, ppm, CDCl ₃ ) 23.9, 25.0 (CH ₃ ), 36.7 (-C-), 42.4 (SCH ₂ ), 69.5 (OCH ₂ ), 125.3, 125.46, 125.47, 126.9, 128.1, 128.8 (CH =), 131.7, 132.9, 134.
5 135.1 (-C =)

(5) (R) -2,2'-bis (2,2-dimethyl-3-methanesulfonylpropylthio) -1,1 '
-Synthesis of binaphthalene: (R) -2,2'-bis (2,2-dimethyl-3-hydroxypropylthio) -1,1'-binaphthalene 1.60 g (3 .26 mmol) to 20 ml of pyridine
The resulting mixture is dissolved in water, 1.43 g (8.15 mmol) of methanesulfonyl chloride is added with stirring at 0 ° C. (ice bath), and the mixture is stirred overnight.

The reaction mixture is cooled to 0 ° C. and 5% hydrochloric acid 1
00 ml was added, the mixture was extracted with ether, and the ether layer was washed with 5% hydrochloric acid and water in this order. After drying over anhydrous magnesium sulfate, the ether was distilled off, and the residue was purified by silica gel column chromatography (developing solvent: chloroform) to obtain 1.81 g (yield 86%) of the title compound as a white solid.

Melting point: 114 to 115 ° C. [α] _D : -9.6 ° (c = 1.0 CHCl ₃ ) EI-MS (70 eV): 646 (M ⁺ ).

¹ HNMR (δ, ppm, CDCl ₃ ): 0.90 (s, 6H, CH ₃ ) 0.92 (s, 6H, CH ₃ ) 2.67 (s, 6H, CH ₃ SO ₂ ) 2 .90 (d, J = 12.8, 2H, SCH ₂ ) 3.00 (d, J = 12.8, 2H, SCH ₂ ) 3.78 (s, 4H, OCH ₂ )

6.98 (d, J = 8.3, 2H, ArH) 7.24 (dd, J = 8.3, 8.3, 2H, ArH) 7.42 (dd, J = 8.3) , 8.3, 2H, ArH) 7.68 (d, J = 8.8, 2H, ArH) 7.88 (d, J = 8.3, 2H, ArH) 7.94 (d, J = 8 .8, 2H, ArH)

¹³ CNMR (δ, ppm, CDCl ₃ ) 23.98, 24.01 (CH ₃ ), 35.9 (-C-),
36.6 (CH ₃ SO ₂ ), 41.8 (SCH ₂ ), 75.9 (OC
H ₂ ), 125.5, 125.7, 125.9, 127.0,
128.1, 128.7 (CH =), 131.8, 132.
8, 134.8, 135.1 (-C =)

(6) (R, R) -2,3; 4,5; 11,1
2; 13,14-Tetra (1,2-naphtho) -8,8,17,
17-Tetramethyl-1,6,10,15-tetrathiacyclooctadeca-2,4,11,13-tetraene (Bi
Synthesis of naph ₂ Me ₄ [18] S ₄ ): under nitrogen stream, 1
In a 000 ml three-necked flask, add 1.43 of cesium carbonate.
suspension of g (4.39 mmol) in anhydrous DMF 700
In ml, (R) -1,1'-binaphthalene-2,2'-dithiol 0.64 g (2.00 mmol) and (R) -2,
2'-bis (2,2-dimethyl-3-methanesulfonylpropiothio) -1,1'-binaphthalene 1.29 g (2.
(100 mmol) of anhydrous DMF liquid (100 ml) was added dropwise at 75 ° C. (oil bath) over 5 hours, and the mixture was stirred at that temperature for 5 days.

After completion of the reaction, DMF was distilled off under reduced pressure, the residue was extracted from 200 ml of chloroform and 300 ml of water, and further extracted twice with 100 ml of chloroform.
The chloroform solution was washed with water and then dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography (developing solvent: hexane: benzene = 3: 1) and recrystallized three times from benzene-hexane to obtain 1.01 g of the title compound as a white crystal (yield 65%).

Melting point:> 300 ° C. [α] _D : + 548 ° (c = 0.54 CHCl ₃ ) FAB-MS (m / z, 3-nitrobenzyl alcohol): 774 (M ⁺ ).

¹ HNMR (δ, ppm, CDCl ₃ ): 0.86 (s, 12H, CH ₃ ), 2.71 (d, J = 11.9, 4H, CH ₂ ) 3.07 (d, J = 11.9, 4H, CH ₂ ) 6.98 (d, J = 8.5, 4H, ArH)

7.22 (dd, J = 8.5, 8.5, 4H,
ArH) 7.40 (dd, J = 8.5, 8.5, 4H, ArH) 7.48 (d, J = 8.5, 4H, ArH) 7.82 (d, J = 8.5, 4H, ArH) 7.88 (d, J = 8.5, 4H, ArH)

¹³ CNMR (δ, ppm, CDCl ₃ ): 26.9 (CH ₃ ), 36.3 (-C-), 44.8 (CH
₂ ), 125.2, 125.5, 125.8, 126.7, 1
28.0, 128.3 (CH =), 131.5, 133.2,
134.7, 135.2 (-C =)

Example 2 Synthesis of Ru complex: K ₂ [RuCl ₅ (H ₂
O)] (manufactured by Aldrich) and 0.056 g (R,
In addition R) -Binaph ₂ Me ₄ (18) S ₄ to 0.116g of 2-methoxyethanol 20 ml, and heated to reflux for 48 hours. After the solvent was distilled off under reduced pressure, the product was purified by silica gel column chromatography (developing solvent: CHCl ₃ ). Recrystallized from CH ₂ Cl ₂ -hexane to give red crystals of trans-RuCl ₂ {(R, R) -Binaph ₂ M
e ₄ [18] S ₄ } 0.111 g was obtained (yield 78%).

Melting point:> 300 ° C. [α] _D : + 28.3 ° (c = 0.71, CHCl ₃ ) FAB-MS (m / z, 3-nitrobenzyl alcohol): 946 ([M + 2] ⁺ ). , 944 (M ⁺ )

¹ HNMR (δ, ppm, CDCl ₃ ): 1.16 (s, 12H, CH ₃ ), 2.86 (d, J = 11 Hz, 4H, CH ₂ ) 3.61 (d, J = 11 Hz) , 4H, CH ₂ ) 6.89 (d, J = 7.8, 4H, ArH)

7.16 (dd, J = 7.8, 7.8, 4H,
ArH) 7.43 (dd, J = 7.8, 7.8, 4H, ArH) 7.62 (d, J = 9.2, 4H, ArH) 7.89 (d, J = 7.8, 4H, ArH) 7.90 (d, J = 9.2, 4H, ArH)

¹³ CNMR (δ, ppm, CDCl ₃ ): 29.4 (CH ₃ ), 34.0 (-C-), 46.2 (CH
₂ ), 125.5, 125.7, 126.1, 126.5, 1
27.5, 128.5 (CH =), 132.6, 132.8,
132.9, 137.0 (-C =)

Example 3 Synthesis of (S) -1-phenylethanol (via asymmetric hydrosilylation reaction): New Experimental Chemistry Course, Vol. 12, No. 193-
RhC according to the reaction described on page 210 (published by Maruzen Co., Ltd.)
l ₃ .3H ₂ O (manufactured by Aldrich) is reacted with cyclooctene (C ₈ H ₁₄ ) to give [RhCl (C ₈ H ₁₄ ) ₂ ] ₂
I got

Then, in a nitrogen atmosphere, [RhCl (C ₈
H _{14) 2] 2} 50 mg and (0.1mmol) (R, R) -
Binaph ₂ Me ₄ [18] S ₄ 154 mg (0.2 m
After stirring a THF solution of (mol) for 0.5 hours at room temperature, 1200 mg (10 mmol) of acetophenone and 2944 mg (16 mmol) of Ph ₂ SiH ₂ were added,
Stir for another 20 hours. This optically active alkoxysilane formation reaction solution was continuously treated with methanol at 0 ° C.
20 ml of 1N hydrochloric acid was added and hydrolyzed, and the product (S) -1-phenylethanol was extracted with methylene chloride.

The product yield and optical purity were determined by GLC (PE
G20M) and HPLC (Product name "CHIRALCEL
OD "manufactured by Daicel Chemical Industries, Ltd., mobile phase: 1% isopropanol / hexane solvent). In addition, the product was purified by silica gel column chromatography (20% benzene / hexane solvent) and then purified by Kugelrohr (Kugel).
rohr) Distilled and isolated. Yield 68%, optical purity 71% ee.

[0064]

INDUSTRIAL APPLICABILITY The novel crown thioether compound of the present invention is excellent as a ligand for a catalyst for asymmetric synthesis and forms a complex with a metal element such as rhodium or ruthenium, and these complexes are asymmetrically alkylated. As a catalyst for asymmetric synthesis such as asymmetric silylation and asymmetric formylation, it exhibits excellent performance in terms of reaction selectivity, conversion rate, catalytic activity, optical purity in asymmetric synthesis.

Further, the alcohol obtained by further hydrolyzing the silyl compound obtained by the asymmetric hydrosilylation reaction using the transition metal-crown thioether complex of the present invention is the silyl compound obtained by the asymmetric hydrosilylation reaction. Since the configuration of the compound is retained as it is,
It is possible to selectively obtain the desired optically active alcohol. that's all

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07F 11/00 9450-4H C07F 11/00 B 13/00 9450-4H 13/00 A 9450-4H Z 15/00 9450-4H 15/00 A 9450-4H B 9450-4H C 9450-4H E 9450-4H F 15/02 9450-4H 15/02 15/03 9450-4H 15/03 15/06 9450- 4H 15/06 // C07B 61/00 300 C07B 61/00 300 C07M 7:00

Claims (5)

[Claims] 1. A compound represented by the general formula (1): Crown thioether represented by. 2. A transition metal-crown thioether complex having the crown thioether compound according to claim 1 as a ligand. 3. The transition metal-crown according to claim 2, wherein the transition metal is iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, chromium, molybdenum, manganese, mercury, copper, silver, gold, platinum or technitium. Thioether complex. 4. The transition metal according to claim 2, wherein the transition metal is ruthenium, rhodium or palladium.
Crown thioether complex. 5. A ketone and a hydrosilane are reacted in an organic solvent in the presence of the transition metal-crown thioether complex according to claim 2, 3 or 4 to form an asymmetric alkoxysilane. Then, a method for producing an optically active alcohol, which comprises acid hydrolysis in a water-soluble organic solvent.