JPH08134064A - New crown thioether, its transition metal complex and asymmetric hydrosilylation using the same - Google Patents

Abstract

PURPOSE: To obtain a new crown thioether useful as a catalyst, excellent in optical purity and selectivity in an asymmetric synthesis. CONSTITUTION: This new crown thioether is expressed by the formula. The compound of the formula is obtained by dissolving 2-amino-3-nitrotoluene in hydrochloric acid, treating the dissolved compound with an aqueous NaNO2 solution, adding KI to bring the compound into 2-iodo-3-nitrotoluene, reacting the compound with copper power in DMF to bring the compound into 2,2'- dimethyl-6,6'-dinitrobiphenyl, which is brought into a racemic modification, optically resolving the racemic modification and treating the obtained optically active compound, etc. The compound of the formula, which is a ligand, can be used as a complex by using transition metals such as iron, cobalt, nickel, ruthenium, rhodium, palladium, mercury, copper, silver, gold, platinum, etc. The transition metal-crown thioether complex can be used in reacting a ketone with a hydroxysilane to obtain an asymmetric alkoxysilane.

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 an asymmetric hydrosilylation method utilizing 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 one after another that have enabled organic synthetic reactions that were impossible by conventional means.

In recent years, various transition metal complexes having crown thioether as a ligand have been synthesized (R. Stephen et al.,
Acc. Chem. Res. 1988, vol. 21, p. 141). However, optically active crown thioethers have been described by RM Kellogg et al. (J. Chem. Soc., Chem. Commun. 1984).
Year, p. 309; Tetrahedron Lett. 1985, 29, 3499.
, But the reaction example of the organic synthesis using the same has been reported, but their metal complexes have not been isolated.

[0004]

As described above, in order to provide a catalyst having higher performance as a catalyst for an asymmetric synthesis reaction, a special crown thioether has been developed up to now, but these are also targets. Depending on the substrate and reaction to be performed, in terms of selectivity, conversion rate, catalytic activity, optical purity, etc.,
There were cases where I was not fully satisfied. Therefore, it is an object of the present invention to provide a new crown thioether compound which gives a complex having a higher catalytic ability than conventional catalysts.

[0005]

[Means for Solving the Problems] In such an actual situation, the present inventor has conducted diligent research to develop the above problems, and as a result,
A transition metal complex having an optically active crown thioether having an atropisomeric 2,2′-vitryl skeleton represented by the following formula (1) as an asymmetric source is a conventionally known optically active crown thioether transition metal complex. In comparison, they found that they are superior in optical purity and selectivity in asymmetric synthesis, and 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.

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

Embedded image

That is, 2-amino-3-nitrotoluene (2) is dissolved in hydrochloric acid and treated with an aqueous sodium nitrite solution, and potassium iodide is added to obtain 2-iodo-3-nitrotoluene (3). Then, copper powder is allowed to act on this compound (3) in DMF, and 2,2′-dimethyl-6,
6'-Dinitrobiphenyl (4) is obtained. The obtained compound (4) is reduced under a hydrogen atmosphere in ethanol using palladium carbon as a catalyst to lead to racemic 2,2′-dimethyl-6,6′-diaminobiphenyl (5).

The obtained racemic compound (5) was optically resolved using tartaric acid to give an optically active 2,2'-dimethyl-6,6'-diaminobiphenyl in the (R) -form or the (S) -form. (6) is obtained. Next, the optically active compound (6) is dissolved in hydrochloric acid, sodium nitrite is added, and dithiocarbonate O- is added.
Aqueous solution of ethyl potassium was added dropwise to 2,2'-dimethyl-
It is 6,6′-bis (O-ethyldithiocarbonyl) biphenyl (7). This compound (7) is reduced with lithium aluminum hydride in diethyl ether to give optically active 2,2'-dimethyl-6,6'-dimercaptobiphenyl (8).

To this optically active compound (8), sodium ethoxide was used as a base, and 3-bromo-2,2-dimethyl-1-propanol was added to obtain 2,2'-dimethyl-.
This leads to 6,6'-bis (2,2-dimethyl-3-hydroxypropylthio) biphenyl (9). The hydroxyl group of this compound (9) is mesylated to form 2,2′-dimethyl-6,
6'-bis (2,2-dimethyl-3-methanesulfonylpropylthio) biphenyl (10) was prepared, and cesium carbonate and another molecule (6) were added in DMF to prepare the crown thioether compound (1) of the present invention. ) Is manufactured.

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, 365. To a known method such as the method described on page 414 (1981), or a method analogous 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 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) 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) Cl ₂ ] ClO ₄ [Ru (L) Cl ₂ ] PF ₆ [Ru (L) Cl ₂ ] BF ₄

Co (L) Cl ₂ [Co (L) Cl ₂ ] (BF ₄ ) ₂ [Co (L) Cl ₂ ] (ClO ₄ ) ₂ [Co (L) Cl ₂ ] (PF ₆ ) ₂ [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 biphenyl skeleton of the crown thioether compound (1) of the present invention has an optically active compound, a racemic compound, and a meso compound, but the present invention includes any of these optical isomer compounds.

The transition metal-crown thioether complex of the present invention can be used, for example, as a catalyst for asymmetric hydrosilylation reaction of ketones and a catalyst for asymmetric synthesis such as asymmetric alkylation and asymmetric formylation.

Of these, the hydrosilylation reaction is specifically carried out in the presence of a transition metal crown ether complex, preferably platinum, a rhodium complex, acetophenone, propiophenone, isopropyl phenyl ketone, t-butyl phenyl ketone, methyl ethyl ketone, As a silylating agent, ketones such as methyl propyl ketone, methyl t-butyl ketone, and methyl benzyl ketone, for example, diphenylsilane, phenylmethylsilane, dichloromethylsilane, diethylsilane, α-naphthylphenylsilane, triethoxysilane, triethylsilane are used. , Trimethylsilane, dimethylphenylsilane and other hydrosilanes are reacted in an organic solvent such as tetrahydrofuran and dioxane. The silylated product obtained by this method can be further hydrolyzed with an acid such as dilute hydrochloric acid in a water-soluble organic solvent such as methanol or ethanol to give an alcohol.

Then, one of the optical rotatory (+) isomers and the optical rotatory (−) isomers of the crown thioether compound of the present invention is selected, and the transition metal-crown thioether is used as a ligand. By using the complex as a catalyst, an asymmetric compound can be synthesized, and a desired product having a desired absolute configuration can be obtained with high optical purity.

[0023]

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 is as follows. ¹ H-NMR JEOL-GX500 ¹³ C-NMR JEOL-GX500 MASS JEOL JMS-AX500 IR JASCO FT / IR-5300 Optical rotation JASCO DIP-370 Melting point Yanako micro melting apparatus Also, in the following Examples, Crown thioether compound (2,3: 4,5,11,1) represented by formula (1)
2: 13,14-Tetra (3'-methyl-1 ', 2'-benzo) -8,8,17,17-tetramethyl-1,6,10,1
5-tetrathiacyclooctadeca-2,4,11,13-
Tetraene) is represented as Bitol ₂ Me ₄ [18] S ₄ .

Example 1 (1) Synthesis of 2-iodo-3-nitrotoluene: In a 1-liter three-necked flask,
50 g of 2-amino-3-nitrotoluene (0.329 m
ol) is dissolved in 600 ml of 6N hydrochloric acid, and -1 is added to this solution.
27.3 g (MW6) of sodium nitrite at 0 ° C (ice-salt)
50 ml of an aqueous solution of 9.00, 0.395 mol) is added dropwise, and the mixture is stirred for another 30 minutes. Next, 200 g of potassium iodide (MW166.00, 1.
(205 mol) aqueous solution (300 mol) is added, and the reaction solution is gradually added thereto with stirring at 0 ° C over 30 minutes, and then stirred at 50 ° C for 30 minutes.

The reaction mixture was extracted with benzene and washed with water, sodium thiosulfate and water in this order. After drying over anhydrous magnesium sulfate and distilling off benzene, the residue was purified by silica gel column chromatography (developing solvent, benzene) and recrystallized from benzene to give the title compound as a lemon-colored crystal 84.
1 g (yield 97%) was obtained.

Melting point: 62-63 ° C. ¹ H-NMR (δ, ppm, CDCl ₃ ) 2.58 (s, 3H, CH ₃ ), 7.35 (dd, J = 8.0,
8.0Hz, 1H, ArH), 7.426 (d, J = 8.0H
z, 1H, ArH), 7.428 (d, J = 8.0 Hz, 1
H, ArH)

(2) Synthesis of 2,2'-dimethyl-6,6'-dinitrobiphenyl: 83.8 g of 2-iodo-3-nitrotoluene in a 300 ml flask under a nitrogen stream.
(0.319mol) and copper powder 40.3g (0.634m)
ol) is dissolved in 400 ml of anhydrous DMF, and the temperature is 160 ° C.
Stir for 2 days (in a silicone oil bath). Then, the temperature is returned to room temperature, benzene is added, and the mixture is filtered through Celite. The filtrate was washed with 1N-hydrochloric acid and water, dried over anhydrous magnesium sulfate, and benzene was distilled off. This was purified by silica gel column chromatography (developing solvent; benzene) and recrystallized from ethanol water to give the title compound as yellow needle crystals 37.
6 g (yield 87%) was obtained.

Melting point: 110-112 ° C. ¹ H-NMR (δ, ppm, CDCl ₃ ) 1.99 (s, 6H, CH ₃ ), 7.48 (dd, J = 8.0,
8.0Hz, 2H, ArH), 7.58 (d, J = 8.0H
z, 2H, ArH), 8.00 (d, J = 8.0 Hz, 2H,
ArH)

(3) Synthesis of 2,2'-dimethyl-6,6'-diaminobiphenyl: 2,2'-dimethyl-6,6'-dinitrobiphenyl in a 2-liter three-necked flask under normal pressure of hydrogen. 31.5 g (0.148 mol) of ethanol 1
Dissolve in 000 ml, add 2.04 g of palladium on carbon (5% palladium), and stir at room temperature for 2 days. After filtration through celite, recrystallization from ethanol gave 21.34 g (yield 88%) of the title compound as white crystals.

Melting point: 158-159 ° C. ¹ H-NMR (δ, ppm, CDCl ₃ ): 1.97 (s, 6
_{H, CH 3), 2.85 (} br, 2H, NH 2), 3.49
(S, 2H, NH ₂ ), 6.66 (d, J = 7.9 Hz, 2H,
ArH), 6.73 (d, J = 7.3 Hz, 2H, ArH),
7.09 (dd, J = 7.9, 7.3Hz, 2H, ArH)

(4) Optical resolution of 2,2'-dimethyl-6,6'-diaminobiphenyl: 2,2'-dimethyl-6,6'-diaminobiphenyl in a 500 ml Erlenmeyer flask.
16.345 g (0.076 mol) of anhydrous ethanol 9
Heat to 7 ml to melt. To this, 11.44 g (0.076 mol) of (1)-(+) tartaric acid dissolved in 58 ml of anhydrous ethanol by heating in a separate container was added, and the mixture was allowed to stand at room temperature overnight. Precipitated white crystals were filtered off, (1)-
(188) 12.188 g of the (R) tartrate salt was obtained. The filtrate has (1)
-(S) tartrate is included.

The crystals separated by filtration were recrystallized twice from absolute ethanol and purified to obtain 0.781 g of white powder. Of this, 0.15 g was hydrolyzed with a 1N aqueous sodium hydroxide solution, extracted with ether, dried over anhydrous magnesium sulfate, and filtered to obtain 72 mg of diamine. Further, this was recrystallized twice with absolute ethanol to give 13 mg of colorless plate crystals.
I got This is (R) -2,2'-dimethyl-6,
It was 6'-diaminobiphenyl. [Α] _D ²⁵ : + 47.8 ° (c = 1.01, EtOH)

On the other hand, the filtrate containing the (1)-(S) tartrate salt is concentrated and recrystallized with absolute ethanol. The filtrate separated by filtration was concentrated to obtain 10.783 g of pale yellow crystals. Of this, 0.52 g is hydrolyzed with a 1N aqueous sodium hydroxide solution and extracted with ether. The extract was dried over anhydrous magnesium sulfate and filtered to obtain 251 mg of diamine. Further, it was recrystallized once with absolute ethanol to give pale yellow crystals.
mg was obtained. This is (S) -2,2'-dimethyl-
It was 6,6'-diaminobiphenyl. [Α] _D ²⁴ : -38.5 ° (c = 1.01, EtOH)

(5) Optically active 2,2'-dimethyl-6,
Measurement of optical purity of 6'-diaminobiphenyl: The (R) form and (S) form obtained by optical resolution were used as an optically active HP.
H using LC column (CHIRALCEL OD)
PLC (mobile phase: 1% isopropanol / hexane)
Then, the optical purity was examined.

The results are shown in FIG. 1. The optical purity of the (R) -form was 92%, and the optical purity of the (S) -form was 81%. In addition, from the two results of the measurement result of the degree of illuminance and Chem. Ber. (Chem. Ber.) 60, 1425 (1927) and Tetrahedron, 30, 1671 (1974), (R )-(+),
It was determined to be (S)-(-).

(6) Synthesis of 2,2'-dimethyl-6,6'-bis (O-ethyldithiocarboxyl) biphenyl:
In a 100 ml three-necked flask, 4.224 g (1) of (R) -2,2'-dimethyl-6,6'-diaminobiphenyl
9.90 mmol) in 5.3 ml of 18N hydrochloric acid,
At −10 ° C. (ice-salt), 10 ml of an aqueous solution of 3.31 g of sodium nitrite is added dropwise over 20 minutes, and the mixture is stirred. Then, in a 300 ml three-necked flask, the reaction solution was added dropwise to 20 ml of an aqueous solution of 12.81 g (79.92 mmol) of O-ethylpotassium dithiocarbonate at 50 ° C. (water bath) while observing the state and stirred.

After completion of dropping, stirring is continued for 30 minutes, the temperature is returned to room temperature, and the mixture is extracted with ether. After drying over anhydrous magnesium sulfate and distilling off the ether, silica gel column chromatography (developing solvent: hexane, hexane: benzene = 9:
Purified by 1, 4: 1, 2: 1, 1: 1, benzene), and the title compound was 2.458 g (yield 29%) as orange crystals.
I got

Melting point: 133 ° C. [α] _D ²⁵ : -197 ° (c = 1.0, EtOH) ¹ H-NMR (δ, ppm, CDCl ₃ ): 1.29 (t, J
= 7.0 Hz, 6H, CH ₃ ), 1.94 (s, 6H, ArCH
₃ ), 4.47-4.59 (m, 4H, CH ₂ ), 7.33 (m,
4H, ArH), 7.50 (dd, J = 3.0Hz, 2H, A
rH) FT-IR (cm ⁻¹ , KBr): ν (C = S) 1225,
ν (CO) 1042 EI-MS (70 eV, m / e): 421 ([M] ⁺ ).

(7) (R) -2,2'-dimethyl-6,6 '
-Synthesis of dimercaptobiphenyl: 100 under nitrogen stream
(R) -2,2'-dimethyl-in a ml eggplant flask
2.06 g (4.92 mmol) of 6,6 '-(O-ethyldithiocarboxyl) biphenyl was dissolved in 30 ml of ether, and lithium aluminum hydride 1.868 g (M
W37.96, 49.21 mmol) in 28 ml of ether
, And slowly added dropwise at 0 ° C. (ice) and stirred.
After the completion of dropping, the stirring is continued for 30 minutes, the temperature is returned to room temperature, and the stirring is continued overnight. Then, the mixture is refluxed for 1 hour, and 30 ml of methanol is added dropwise at 0 ° C. (ice) to treat the remaining lithium aluminum hydride. 5% Hydrochloric acid-ether and 12N-hydrochloric acid-ether were added in this order for extraction and washing with water. The extract was dried over anhydrous magnesium sulfate, the ether was distilled off, and the residue was recrystallized from hexane to give the title compound as white needle crystals 1.0
9 g (yield 90%) was obtained.

Melting point: 110 ° C. [α] _D ²⁵ : -17 ° (c = 1.0, EtOH) ¹ H-NMR (δ, ppm, CDCl ₃ ): 1.98 (s, 6
H, CH ₃ ), 3.15 (s, 2H, SH), 7.11 (d,
J = 7.6 Hz, 2H, ArH), 7.16 (dd, J = 7.
8,7.8Hz, 2H, ArH), 7.27 (d, J = 7.6)
Hz, 2H, ArH) FT-IR (cm ^-1 , KBr): ν (SH) 255
6 EI-MS (70 eV, m / e): 246 ([M] ⁺ ),
213 ([M-SH] ⁺ )

(8) (R) -2,2'-dimethyl-6,6 '
-Synthesis of bis (2,2-dimethyl-3-hydroxypropylthio) biphenyl: In a 300 ml eggplant-shaped flask under a nitrogen stream, 60 ml of ethanol and 5 parts of metallic sodium were added.
00 mg (MW 23.00, 21.74 mmol) is added to prepare an ethanol solution of sodium ethoxide. 2,2'-Dimethyl-6,6'-dimercaptobiphenyl 2.131 g (8.649 mmol) was added to ethanol.
Dissolve in 80 ml, add with pyridine and stir for 1 hour.
3-Bromo-2,2-dimethyl-1-propanol 8
ml (d = 1.358, 65.03 mmol) was added and 1
Reflux overnight at 00 ° C. (oil bath).

After concentration, water is added to treat the remaining sodium ethoxide, and the mixture is extracted with ether. After drying over anhydrous magnesium sulfate and removing the ether by distillation, the residue was purified by silica gel column chromatography (developing solvent: benzene, chloroform, ether). Recrystallized from methanol,
When cooled at -70 ° C (methanol, dry ice),
0.26 g (yield 62%) of the title compound as orange crystals.
I got

Melting point: 58-60 ° C. [α] _D ²⁵ : -12 ° (c = 1.0, CHCl ₃ ) ¹ H-NMR (δ, ppm, CDCl ₃ ): 0.87 (s, 6
H, CH ₃ ), 1.01 (s, 6H, CH ₃ ), 1.93 (s,
6H, ArCH ₃ ), 2.82 (d, J = 11.6 Hz, 2
H, CH ₂ ), 2.85 (s, 2H, OH), 2.96 (d, J
= 11.6 Hz, 2H, CH ₂ ), 3.15 (d, J = 11.1.
6Hz, 2H, CH ₂ ), 3.43 (d, J = 11.6Hz,
2H, CH ₂ ), 7.10 (d, J = 7.1Hz, 2H, Ar
H), 7.26 (m, 4H, ArH)

(9) (R) -2,2'-dimethyl-6,6 '
-Synthesis of bis (2,2-dimethyl-3-methanesulfonylpropylthio) biphenyl: 100 ml under nitrogen stream
(R) -2,2'-dimethyl-6,6 'in an eggplant flask of
-Bis (2,2-dimethyl-3-hydroxypropylthio) biphenyl 2.117 g (5.06 mmol) was dissolved in 20 ml of pyridine, and methanesulfonyl chloride 1.5 ml (d = 1.480, 19) was added at 0 ° C (ice). .38 mmo
Add 1) and stir overnight. Ice water was added to the reaction mixture, extraction was performed with chloroform, and pyridine in the organic layer was washed with 5% hydrochloric acid and water in this order. After drying over anhydrous magnesium sulfate and distilling off chloroform, the residue was purified by silica gel column chromatography (developing solvent; benzene, chloroform) to give 2.47 g of the title compound as a yellow solid (crude yield: 8
5%).

Melting point: 97-98 ° C. ¹ H-NMR (δ, ppm, CDCl ₃ ): 1.023 (s,
6H, CH ₃ ), 1.027 (s, 6H, CH ₃ ), 1.92
(S, 6H, ArCH ₃ ), 2.85 (d, J = 12.6H
z, 2H, CH ₂ ), 2.89 (s, 6H, SCH ₃ ), 2.9
4 (d, J = 12.6 Hz, 2H, CH ₂ ), 3.92 (d, J
= 9.4 Hz, 2H, CH ₂ ), 3.96 (d, J = 9.4H
z, 2H, CH ₂ ), 7.10 (d, J = 7.0 Hz, 2H, A
rH), 7.22-7.27 (m, 4H, ArH) ¹³ C-NMR (δ, ppm, CDCl ₃ ): 19.73 (C
_{H 3 Ar), 24.09 (CH} 3), 35.81 (-C
-), 36.92, 41.10 (CH 2), 76.05 (S
_{-CH 3), 124.14,127.16, 128.07 (} =
CH), 136.37, 137.19, 137.99 (=
C) EI-MS (70 eV, m / e): 574 ([M] ⁺ ).

(10) (R, R) -Bitol ₂ Me
₄ Synthesis of [18] S ₄ : 4.56 g of cesium carbonate (MW325.
82, 14.00 mmol) anhydrous DMF suspension 70
In 0 ml, 1.44 g (5.84 mmol) of (R) -2,2'-dimethyl-6,6'-dimercaptobiphenyl and (R) -2,2'-dimethyl-6,6'-bis (2 , 2-Dimethyl-3-methanesulfonylpropylthio) biphenyl 3.36 g (5.85 mmol) in anhydrous DMF solution 1
After dropping 50 ml at 75 ° C. (oil bath) over 5 hours,
Stir at that temperature.

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 recrystallized from hexane three times to obtain (R, R) -Bitol ₂ Me ₄ as a white solid.
0.81 g (yield 22%) of [18] S ₄ was obtained.

Further, (S) -2,2'-dimethyl-6,6 '
-Using dimercaptobiphenyl and (S) -2,2'-dimethyl-6.6'-bis (2,2-dimethyl-3-methanesulfonylpropylthio) biphenyl in the same manner as above (S, S) -The body is (R) -2,2'-dimethyl-6,
An (R, S) -form was obtained from 6'-dimercaptobiphenyl and (S) -2,2'-dimethyl-6.6'-bis (2,2-dimethyl-3-methanesulfonylpropylthio) biphenyl. .

(R, R) -body and (S, S) -body Melting point: 168-169 ° C (R, R) 167-168 ° C (S, S) [α] _D ²⁵ : + 152 ° (c 0 .42, hexane) (R, R) -157 ° (c 0.38, hexane) (S, S) ¹ H-NMR (δ, ppm, CDCl ₃ ): 0.97 (s, 1)
2H, CH ₃ ), 1.92 (s, 12H, ArCH ₃ ), 2.
65 (d, J = 11.6 Hz, 4H, CH ₂ ), 2.85 (d,
J = 11.6 Hz, 4H, CH ₂ ), 7.06 (d, J = 7.
6Hz, 4H, ArH), 7.11 (d, J = 7.6Hz, 4
H, ArH), 7.18 (dd, J = 7.6, 7.6 Hz, 4
H, ArH) ¹³ C-NMR (δ, ppm, CDCl ₃ ): 19.72 (C
_{H 3 Ar), 26.97 (CH} 3), 35.72 (-C
_{-), 44.35 (CH 2)} , 124.89, 126.79,
127.71 (= CH), 137.05, 137.11,
138.60 (= C) EI-MS (70 eV, m / e): 628 ([M] ⁺ ).

(R, S) -body Melting point: 282-283 ° C. ¹ H-NMR (δ, ppm, CDCl ₃ ): 0.77 (s, 6)
H, CH ₃ ), 1.05 (s, 6H, CH ₃ ), 1.91 (s,
12H, ArCH ₃ ), 2.52 (d, J = 11.8 Hz, 4
H, CH ₂ ), 3.01 (d, J = 11.8 Hz, 4H, C
H ₂ ), 7.03 (d, J = 7.8 Hz, 4H, ArH),
7.09 (d, J = 7.8Hz, 4H, ArH), 7.18
(Dd, J = 7.8, 7.8 Hz, 4H, ArH) ¹³ C-NMR (δ, ppm, CDCl ₃ ): 19.72 (C
H ₃ Ar), 23.85, 28.26 (CH ₃ ), 36.7
2 (-C-), 45.54 (CH 2), 125.46, 1
27.04, 127.67 (= CH), 136.63, 1
37.34, 139.00 (= C) EI-MS (70 eV, m / e): 628 ([M] ⁺ ).

Example 2 Synthesis of Ru complex: K ₂ [RuCl ₅ (H ₂
O)] and (R, R) -Bitol ₂ Me ₄ [18] S ₄ are added to 2-methoxyethanol and heated under reflux for 48 hours. After the solvent was distilled off under reduced pressure, the product was purified by silica gel column chromatography (CHCl ₃ developing solvent), and CHCl ₃
Recrystallized from hexane to give pink crystals of trans-ruthenium-2,3: 4,5,11,12: 13,14-tetra (3'-methyl-1 ', 2'-benzo) -8,8 , 17,17
-Tetramethyl-1,6,10,15-tetrathiacyclooctadeca-2,4,11,13-tetraene (hereinafter, t
rans-RuCl ₂ {(R, R) -Bitol ₂ Me
₄ [18] S ₄ }) was obtained (yield 67%).

Melting point:> 300 ° C. [α] _D ²⁵ : + 35 ° (c 1.0, CHCl ₃ ) ¹ H-NMR (d, ppm, CDCl ₃ ): 1.25 (s,
12H, CH ₃ ), 1.91 (s, 12H, CH ₃ ), 2.
74 (d, J = 11 Hz, 4H, CH ₂ ), 3.45
(D, J = 11 Hz, 4H, CH ₂ ), 7.19-7.26
(M, 12H, aromatic). ¹³ C-NMR (d, ppm, CDCl ₃ ): 19.8 (C
_{H 3), 29.3 (CH 3} ), 33.8 (-C-), 46.
2 (CH ₂ ), 126.3, 127.0, 129.9 (= C
H), 135.8, 135.9, 136.9 (= C-). IR (cm ^-1 , CsI): ν (Ru-Cl) 270 FAB-MS (m / z, 3-NOBA): 802
(M ⁺ )

Example 3 Synthesis of Co complex: [Co (CH₃C
N)₆] (BF_Four)₂And (R, R) -Bitol₂ Me_Four[1
8] S_FourDissolve in nitromethane and stir at 60 ℃ for 8 hours
mix. After filtering the reaction solution, the solvent was concentrated under reduced pressure,
A small amount of ether was added, and dark brown crystalline cobalt-2,
3: 4,5: 11,12: 13,14-Tetra (3'-meth)
Ru-1 ', 2'-benzo) -8,8,17,17-tetramethy
Ru-1,6,10,15-tetrathiacyclooctadeca-
2,4,11,13-tetraene bistetrafluorobo
Rate (hereinafter, [Co {(R, R) -Bitol₂Me_Four
[18] S_Four}] (BF_Four)₂Was obtained (yield 71
%).

[Α] _D ²⁵ : + 331 ° (c 1.0, CH ₃ CN) FAB-MS (m / z, 3-NOBA): 687
(M ⁺ ).

Then, the obtained [Co {(R, R) -B
Itol ₂ Me ₄ [18] S ₄ }] (BF ₄ ) ₂ is dissolved in nitromethane, 6 equivalents of LiCl are added, and the mixture is stirred in air at room temperature for 12 hours. After filtering the reaction solution, the solvent was concentrated under reduced pressure, a small amount of ether was added, and a tan crystal of brown crystals was added.
s- [CoCl ₂ {(R, R) -Bitol ₂ Me ₄ [1
8] S ₄ }] (BF ₄ ) ₂ was obtained (yield 80%).

[Α] _D ²⁵ : + 331 ° (c 1.0, CH ₃ CN) FAB-MS (m / z, 3-NOBA): 757
^{. (M +), 722 (} [M-Cl] +) 1 H-NMR (d, ppm, acetone -d _6): 1.16
(S, 12H, CH ₃ ), 1.90 (s, 12H, C
H ₃ ), 2.72 (d, J = 11 Hz, 4H, CH ₂ ),
2.90 (d, J = 11Hz, 4H, CH 2), 7.30-
7.55 (m, 12H, aromatic). ¹³ C-NMR (d, ppm, acetone-d ₆ ): 20.0
_{(CH 3), 28.9 (CH} 3), 34.2 (-C-), 4
7.5 (CH ₂ ), 130.5, 130.7, 133.5
(= CH), 128.6,138.5 (= C-).

Example 4 Asymmetric hydrosilylation reaction: [RhCl 2]
_{(C 8 H 14) 2]} 2 0.1mmol and (R, R) -Bit
A THF solution containing 0.2 mmol of ol ₂ Me ₄ [18] S ₄ was stirred at room temperature for 0.5 hours, and then acetophenone 10 m
mol and diphenylsilane (Ph ₂ SiH ₂ ) 16 mmo
Add 1 and stir for 20 hours. After completion of the reaction, 10 ml of methanol and then 20 ml of 1N-hydrochloric acid were added at 0 ° C. for hydrolysis, and the product (S) -1-phenylethanol was extracted with methylene chloride.

The product yield and optical purity were determined by GLC.
(PEG 20M) and HPLC (Daicel CHIR
ALCEL OD, 1% isopropanol / hexane solvent) was used. In addition, after purifying the product by silica gel column chromatography (20% benzene / hexane solvent),
It was isolated by Kugelrohr distillation (yield 35%, optical purity 57% ee).

[0060]

EFFECTS OF THE INVENTION The crown thioether compound (1) of the present invention is excellent as a ligand of a catalyst for asymmetric synthesis and forms a complex with a metal element such as rhodium or ruthenium. The obtained crown thioether-metal complex exhibits excellent performance as a catalyst for asymmetric synthesis such as asymmetric alkylation, asymmetric silylation and asymmetric formylation, and can be advantageously used for asymmetric synthesis reactions. is there.

[Brief description of drawings]

FIG. 1 is a drawing showing the results of examining the optical purity of the optically resolved 2,2-dimethyl-6,6′-dimethylbiphenyl (R) form and (S) form.

Claims (4)

[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 is selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, chromium, molybdenum, manganese, mercury, copper, silver, gold, platinum and technitium. Transition metal-crown thioether complex of. 4. A method for hydrosilylation of reacting a ketone with hydrosilane to obtain an alkoxysilane, wherein the transition metal-crown thioether complex according to claim 3 is used to obtain an asymmetric alkoxysilane. Method.