JPH11335385A - Transition metal complex and production of optically active alcohol using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound industrially useful as a catalyst for hydrogen transfer type reductive reaction. SOLUTION: This new compound is expressed by the formula (R is H, methyl or the lie; M is Rh, Ir or Co; R<1> is methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl or the like; R<2> is cyclohexyl, phenyl or the like). The compound of the formula is obtained by reacting a diamine compound (e.g. 1-methanesulfonyl-1,2-diphenylethylenediamine) with a rhodium, iridium or cobalt complex, e.g. [RhCl2 C5 (CH3 )5 }]2 in the presence of a tertiary amine such as triethylamine or diisopropylethylamine. The compound of the formula can be used advantageously as a catalyst in hydrogen transfer type reductive reactions, e.g. reactions wherein optically active alcohols are produced from aromatic ketones.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel optically active transition metal complex in which an optically active diamine and a pentamethylcyclopentadienyl group or an indenyl group are coordinated, and a method for producing an optically active alcohol using the same.

[0002]

2. Description of the Related Art Conventionally, many transition metal complexes have been used as catalysts for organic synthesis reactions. In particular, noble metal complexes have been widely used despite their high cost because they are stable and easy to handle. ing. Many synthesis studies using transition metal complexes such as noble metal complex catalysts as catalysts have been made, and many reports have been made on organic synthesis reactions which have been impossible with conventional means.

[0003] Among them, the asymmetric hydrogenation reaction for obtaining an optically active alcohol by reducing a carbonyl group has made remarkable progress (R. Noyori, "Asymmetric Catalysis In
Organic Synthesis ", pp. 56-82, 1994, John Wiley &
Sons, Inc.).

However, in the method of asymmetric hydrogenation using a transition metal complex catalyst, an optically active alcohol can be produced with high selectivity, but a pressure-resistant reactor is required to use hydrogen gas as a hydrogen source, and the reaction operation is difficult. And safety issues. Therefore, it has been desired to realize a new method for synthesizing an optically active alcohol using a highly active and selective catalyst without using hydrogen gas.

[0005] Recently, it has been reported that an optically active alcohol compound is obtained from an aromatic ketone by a hydrogen transfer type reduction reaction using a ruthenium complex to which an optically active diamine compound is coordinated and using isopropyl alcohol as a hydrogen source ( S. Hahiguchi et al., J. Am. Chem. Soc., 1995,
117, 7562).

[0006]

As described above, it is desired to supply an industrially usable complex as a catalyst for a hydrogen transfer type reduction reaction, and it is an object of the present invention to satisfy these needs. It is assumed that.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies on a complex having a catalytic activity in a hydrogen transfer type reduction reaction, and as a result, a complex in which an optically active diamine is coordinated to rhodium, iridium, or cobalt metal. Was found to be excellent in a hydrogen transfer type reduction reaction, and completed the present invention.

That is, the present invention provides the following (I) to (III)
The present invention provides a novel transition metal complex having a catalytic ability in a hydrogen transfer type reduction reaction shown in (1). (I) General formula (1)

[0009]

Embedded image

(Wherein R may be hydrogen, a methyl group or two adjacent Rs may be bonded together to form a 6-membered heterocyclic ring. M represents Rh, Ir, Co, and R ¹ represents methanesulfonyl. A trifluoromethanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group, a naphthalenesulfonyl group, a camphorsulfonyl group, and R ² is a cyclohexyl group, a phenyl group, a phenyl group which may have a substituent, a naphthyl group. Or a cyclohexane ring may be formed with R ² ).

(II) The following general formula (2) produced by treating general formula (1) with a base

[0012]

Embedded image

(Wherein, R, M, R ¹ and R ² have the above-mentioned meanings).

(III) The following general formula (3) produced by treating general formula (2) in isopropanol

[0015]

Embedded image

(Wherein, R, M, R ¹ and R ² have the above-mentioned meanings).

Further, the present invention provides a method for producing an optically active alcohol, which comprises subjecting an aromatic ketone optionally having a substituent to an asymmetric hydrogenation reaction by a hydrogen transfer type reduction reaction in the presence of the transition metal complex. Is provided.

Hereinafter, the present invention will be described in more detail. In the transition metal complexes (1), (2), and (3) of the present invention, as specific examples of R 1, R 2 is a group obtained by bonding two adjacent R 2 together such as hydrogen, methyl, or indenyl. It may form a membered heterocycle. Specific examples of R ¹ include a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group, p- toluenesulfonyl group, naphthalenesulfonyl group, camphor sulfonyl group, etc. are exemplified, R ² is Shikurohekiru group, a phenyl group,
Optionally substituted phenyl, naphthyl, or
R ² may form an alicyclic ring.

The transition metal complex of the present invention can be synthesized by reacting a diamine compound with a rhodium, iridium or cobalt complex in the presence of a tertiary amine such as triethylamine or diisopropylethylamine.

Specific examples of rhodium, iridium and cobalt complexes include [RhCl ₂ ｛C ₅ (CH ₃ ) ₅ ｝] ₂ (hereinafter referred to as [RhC
l ₂ Cp ^* ] ₂ ), [RhCl ₂ (C ₅ H ₅ )] ₂ (hereinafter [RhCl ₂ Cp] ₂
), [RhCl ₂ (C ₉ H ₇ )] ₂ , [IrCl ₂ ｛C ₅ (CH ₃ ) ₅ ｝] ₂ (hereinafter referred to as [IrCl ₂ Cp ^* ] ₂ ), [IrCl ₂ (C ₅ H ₅ )] ₂ (hereinafter [I
rCl ₂ Cp] ₂ ), [IrCl ₂ (C ₉ H ₇ )] ₂ , [CoCl ₂ ｛C ₅ (C
H ₃ ) ₅ ｝] ₂ (hereinafter referred to as [CoCl ₂ Cp ^* ] ₂ ), [CoCl ₂ (C
₅ H _{5)] 2} (hereinafter, [referred to as _{CoCl 2 Cp] 2), [} CoCl 2 (C 9 H 7)] 2,
And the like.

Specific examples of the diamine compound include 1-methanesulfonyl-1,2-diphenylethylenediamine, 1-p-toluenesulfonyl-1,2-diphenylethylenediamine, 1-trifluoromethanesulfonyl-1,2 -Diphenylethylenediamine, 1-camphorsulfonyl-
1,2-diphenylethylenediamine, 1-naphthalenesulfonyl-1,2-diphenylethylenediamine, 1-methanesulfonyl-1,2-cyclohexanediamine, 1-p-toluenesulfonyl-1,2-cyclohexanediamine, 1-trifluoromethanesulfonyl -1,2-cyclohexanediamine,
1-camphorsulfonyl-1,2-cyclohexanediamine, 1-naphthalenesulfonyl-1,2-cyclohexanediamine, 1-methanesulfonyl-1,2-dicyclohexylethylenediamine, 1-p-toluenesulfonyl-1,2-dicyclohexylethylenediamine, Examples include 1-trifluoromethanesulfonyl-1,2-dicyclohexylethylenediamine, 1-camphorsulfonyl-1,2-dicyclohexylethylenediamine, 1-naphthalenesulfonyl-1,2-dicyclohexylethylenediamine, and the like.

The transition metal complex represented by the general formula (2) of the present invention can be preferably produced by treating the transition metal complex represented by the general formula (1) with a base such as potassium hydroxide. . Further, the transition metal complex represented by the general formula (3) can be preferably produced by treating the transition metal complex represented by the general formula (2) in isopropanol.

The general formulas (1) to (3) of the present invention
Can be advantageously used in a hydrogen transfer type reduction reaction. As an example, a reaction for producing an optically active alcohol from an aromatic ketone represented by the following formula will be described below.

[0024]

Embedded image

(Wherein, R ³ represents a hydrogen atom, a lower alkyl group, and R ⁴ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, an amino group, a dimethylamino group, a carboxyl group, a lower alkoxycarbonyl group. , A nitro group, and when R ⁴ is in the ortho position, R ³ and R ⁴ represent 5,6,
It may form a 7-membered cyclo ring. )

Specific examples of the aromatic ketones in the above reaction include acetophenone, propiophenone, 2'-methylacetophenone, 3'-methylacetophenone, 4'-methylacetophenone, 2'-methoxyacetophenone, and 3'-methoxy. Acetophenone, 4'-methoxyacetophenone,
2'-chloroacetophenone, 3'-chloroacetophenone, 4'-chloroacetophenone, 2'-aminoacetophenone, 3'-aminoacetophenone, 4'-aminoacetophenone, 2'-dimethylaminoacetophenone, 3'-dimethylaminoacetophenone, 4'-dimethylaminoacetophenone, 2-acetylbenzoic acid, 3-acetylbenzoic acid,
4-acetylbenzoic acid, methyl 2-acetylbenzoate, methyl 3-acetylbenzoate, methyl 4-acetylbenzoate, 2 '
-Nitroacetophenone, 3'-nitroacetophenone,
4'-nitroacetophenone, 1-indanone, 1-tetralone, 1-benzosuberone, and the like.

The above-described reaction for producing an optically active alcohol compound by hydrogen transfer-type asymmetric reduction is carried out in the presence of a hydrogen-donating compound and a base. The hydrogen-donating compound, which is a hydrogen source for reduction, is an organic or inorganic compound that can supply hydrogen by a thermal action or a catalytic action, and is not particularly limited as long as it has such properties. There is no. Examples of preferred hydrogen donor compounds include alcohol compounds such as methanol, ethanol, isopropanol, 1-propanol, butanol and benzyl alcohol, formic acids such as formic acid, formate and formate, and partially saturated carbon such as tetralin and decalin. Unsaturated hydrocarbons with bonds, heterocyclic compounds, hydroquinones,
Phosphorous acid, and the like. Among these, alcohol compounds, formic acid and ammonium salts thereof are preferred. Particularly, isopropanol and formic acid are preferred.

As the base, potassium hydroxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium tert-butoxide, lithium hydroxide, lithium methoxide, lithium ethoxide, lithium isopropoxide, lithium tertoxide -Butoxide, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium te
rt-butoxide and the like.

In the method of the present invention, a solvent is used if necessary, and examples of the solvent include aromatic compounds such as toluene and xylene, halogen compounds such as methylene chloride, dimethyl sulfoxide, and dimethylformamide. And an organic compound such as acetonitrile. However, when, for example, formic acid or its ammonium salt is used as the hydrogen-donating compound, it is not necessary to use a solvent.

In the above invention, the amount of the transition metal complex used as the catalyst is 0.01 to 10 mol based on the substrate.
%, Preferably about 0.05 to 5 mol%. The amount of the hydrogen-donating compound used may vary depending on the solubility and economics of the reaction substrate, but is usually about 0.1 to 30% by weight, preferably about 0.1 to 10% by weight, based on the substrate. And the amount of base is 20
It is about 0.1-fold mole, preferably about 5-0.5 mole.

Further, the above reaction is usually carried out at 0 to 100 ° C.
Temperature, preferably at a temperature of about 10-50 ° C,
The reaction is completed for about 10 to 100 hours, but these conditions can be appropriately changed depending on the amounts of the reactants used.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

The apparatus used for measuring the physical properties in each embodiment is as follows. ¹ H NMR; JEOL JNM-AL400 ¹ H NMR (400 MHz) Varian MERCURY 300 ¹ H NMR (300 MHz) IR; JASCO FT / IR-230 UV; JASCO V-570 MS; JEOL JMX DX-303HF Melting point measurement; Yanaco MP-52982 Elemental analysis; Perkin Elmer 2400 HPLC; HPLC Pump JASCO PU-980 UV / VIS Detector JASCO UV-970

[0034]

Reference Example 1 Synthesis of di-μ-chlorodichlorobis (pentamethylcyclopentadienyl) diiridium A mixture of iridium chloride pentahydrate (5.67 g, 19 mmol) and pentamethylcyclopentadiene (4.0 g, 29 mmol) was prepared. Heat and reflux in methanol (120 ml) for 19 hours. The reaction mixture was cooled to room temperature, and the precipitated brick-colored solid was collected by filtration, washed with a small amount of ether, and air-dried to obtain a crude product of IrCl ₂ (C ₅ (CH ₃ ) ₅ ] ₂ (4.1 g). The filtrate is evaporated to dryness under reduced pressure and the residue is washed with ether to give an additional 1.72 g of product.
When combined, the yield of the title compound was 5.82 g (yield 76.9
%).

[0035]

Reference Example 2 Synthesis of di-μ-chlorodichlorobis (pentamethylcyclopentadienyl) dirhodium A mixture of rhodium chloride trihydrate (5.0 g, 19 mmol) and pentamethylcyclopentadiene (4.0 g, 29 mmol) was prepared. methanol
(120 ml) and refluxed for 19 hours. The reaction mixture was cooled to room temperature, and the precipitated brick-colored solid was collected by filtration, washed with a small amount of ether, and air-dried to obtain a crude product of [RhCl ₂ (C ₅ (CH ₃ ) ₅ ] ₂ (3.6 g). The filtrate is evaporated to dryness under reduced pressure and the residue is washed with ether to give a further 1.21 g of product, for a total of 5.17 g (88.9%) of the title compound.
It is.

[0036]

Example 1 Synthesis of Cp ^* Ir (TsDPEN) Cl In Schlenk, [Cp ^* IrCl ₂ ] ₂ 163.5 mg (0.205 mmol)
And (S, S) -1-p-toluenesulfonyl-1,2-diphenylethylenediamine ((S, S) -TsDPEN) 150.8 mg (0.411 mmol)
The Schlenk was replaced with argon, 9 ml of THF was added to dissolve it, and then 0.13 ml (0.825 mmol) of Et ₃ N was added to suspend. After stirring for 2 hours, the salt was centrifuged, the solution was transferred to Schlenk and THF was removed in vacuo to give a red-orange powder. After washing twice with 10 ml of hexane and drying under reduced pressure, 290.1 mg
(97% yield). Redissolve in 5 ml of THF, add 30 ml of hexane, and reprecipitate.
(87% yield).

Decomp:> 205 ° C. IR (KBr): 3264, 3212, 3135 (NH), 3060, 3027 (CH
arom), 2967, 2912 (C-Haliph) cm ^-1 UV-vis (CH ₂ Cl ₂ ): λmax = 315.0 (ε = 1.65 x 1
0 ³ ), 281.5 (ε = 6.83 x 10 ³ ) nm Anal.Calcd for C ₃₁ H ₃₆ Cl ₁ Ir ₁ N ₂ O ₂ S ₁ : C, 51.12; H,
. 4.98; N, 3.85% Found :. C, 51.01; H, 5.06; N, 4.03% 1 H NMR (400 MHz, CDCl 3, 35 ℃): δ 1.82 (s, 15
H), 2.24 (s, 3H), 3.70 (m, 1H), 4.00 (br.d, 1H),
4.29 (d, ³ J (H, H) = 10.7 Hz, 1H), 4.51 (br.t, 1H),
6.66-7.47 (14H) FAB-MS: 728 (M ⁺ ), 693 (M ⁺ -Cl)

[0038]

Example 2 Synthesis of Cp ^* Ir (TsDPEN) Schlenk added [Cp ^* IrCl ₂ ] ₂ 54.4 mg (0.068 mmol)
50.0 mg (0.136 mmol) of (S, S) -TsDPEN was taken, the inside of the Schlenk was replaced with argon, and 0.95 ml of CH ₂ Cl ₂ was added to dissolve. The solution was orange. To this solution, add 1M KOH
When 0.95 ml (KOH 0.95 mmol) of the aqueous solution was added, the solution was separated into two layers and the organic layer turned dark purple. After stirring for 1 hour,
The aqueous layer was removed, the organic layer was washed with 3 ml of water, and the solvent was distilled off under reduced pressure. After adding 5 ml of hexane and stirring, the supernatant was removed, and the remaining solid was dried to obtain 75.0 mg (80% yield) of a dark purple powder.

Decomp:> 82 ° C. IR (KBr): 3331 (NH), 3060, 3023 (CH arom), 296
7, 2911, 2865 (CH aliph) cm ^-1 UV-vis (CH ₂ Cl ₂ ): λmax = 537.5 (ε = 3.67 x 1
0 ³ ), 428.5 (ε = 3.38 x 10 ³ ), 378.5 (ε = 2.89 x 1
0 ³ ) nm FAB-MS: 693 (MH ⁺ ) Anal. Calcd for C ₃₁ H ₃₅ Ir ₁ N ₂ O ₂ S ₁ : C, 53.81; H,
. 5.10; N, 4.05% Found :. C, 54.45; H, 5.42; N, 3.58% 1 H NMR (300 MHz, d 8 -toluene, 35 ℃): δ 1.62
(s, 15H), 2.01 (s, 3H), 4.07 (s, 1H), 4.53 (s, 1
H), 4.99 (br. 1H), 6.60, 7.44 (each d, ³ J (H, H) = 8 H
z, 2H), 6.97-7.67 (m, 10H)

[0040]

Example 3 Synthesis of Cp ^* Ir (TsDPEN) H In Schlenk, 264.9 mg (0.382 mmol) of Cp ^* Ir (TsDPEN)
The Schlenk was purged with argon, 10.0 ml of isopropanol was added, and the mixture was stirred. The solution changed from deep purple to pale red, and further changed to yellow. After stirring for 30 minutes, isopropanol was distilled off and the residue was washed with hexane to obtain 258.9 mg (98% yield) of a pale yellow powder.

Decomp: 115-118 ° C. IR (KBr): 3321, 3241, 3154 (NH), 3060, 3023 (CH
arom), 2958, 2908 (CH aliph), 2078 (broad, Ir-H)
cm ^-1 UV-vis (2-propanol): λmax = 301.5 (ε = 5.14 x
10 ⁴ ) nm FAB-MS: 694 (M ⁺ ) Anal. Calcd for C ₃₁ H ₃₇ Ir ₁ N ₂ O ₂ S ₁ : C, 53.66; H,
. 5.37; N, 4.04% Found :. C, 54.42; H, 5.42; N, 3.78% 1 H NMR (300 MHz, d 8 -toluene, 35 ℃): δ -9.94
(s, IH), 2.05 (s, 15H), 2.09 (s, 3H), 3.34 (br,
d, 1H), 3.65 (m, 1H), 4.15 (br.t, 1H), 4.52 (d, ³ J
(H, H) = 8 Hz, 1H), 6.75, 7.74 (each d, ³ J (H, H) = 8 Hz,
2H), 6.83-7.23 (m, 10H)

[0042]

Example 4 Synthesis of Cp ^* Rh (TsDPEN) Cl In Schlenk, [Cp ^* RhCl ₂ ] ₂ 126.0 mg (0.204 mmol)
And (S, S) takes -TsDPEN 150.2mg (0.410 mmol), and the Schlenk with argon, CH ₂ Cl ₂ 10 ml was added, and Et ₃ N
0.11 ml (0.82 mmol) was added and stirred. After stirring for 2 hours, CH ₂ Cl ₂ was distilled off under reduced pressure, THF was added, and the salt was centrifuged. THF was distilled off under reduced pressure and the residue was washed with hexane to obtain 231.5 mg (yield: 88%) of an orange powder.
This was redissolved in 4 ml of CH ₂ Cl ₂ and re-precipitated by adding 20 ml of hexane to give 193.7 mg of orange powder.
(74% yield).

Decomp: 129-131 ° C. IR (KBr): 3284, 3209, 3135 (NH), 3060, 3032 (CH a
rom), 2958, 2912 (CH aliph) cm ^-1 UV-vis (CH ₂ Cl ₂ ): λmax = 351.5 (ε = 4.02 x 10 ³ )
nm FAB-MS: 639 (MH ⁺ ), 603 (M ⁺ -Cl) Anal. Calcd for C ₃₁ H ₃₆ Cl ₁ Rh ₁ N ₂ O ₂ S ₁ : C, 58.26;
. H, 5.68; N, 4.38 % Found:. C, 57.48; H, 5.38; N, 4.42% 1 H NMR (400 MHz, CDCl 3, 35 ℃): δ 1.84 (s, 15H),
2.21 (s, 3H), 3.26 (br, d, 1H), 3.69 (m, 1H), 3.9
5 (d, ³ J (H, H) = 10.7 Hz, 1H), 3.97 (br, t, 1H), 6.65
-7.44 (m, 14H)

[0044]

Example 5 Synthesis of Cp ^* Rh (TsDPEN) Schlenk added [Cp ^* RhCl ₂ ] ₂ 84.9 mg (0.137 mmol)
100.7 mg (0.275 mmol) of (S, S) -TsDPEN was taken, the atmosphere in the Schlenk was replaced with argon, and 2 ml of CH ₂ Cl ₂ was added to dissolve. When 2 ml (2 mmol of KOH) of a 1 M aqueous KOH solution was added to this solution and stirred, the mixture was separated into two layers, and the lower organic layer turned dark green. After stirring for 3 hours, the aqueous layer was extracted, and the solvent was distilled off under reduced pressure. After washing with ether and hexane and evaporating the solvent under reduced pressure, 129 mg of dark green powder (yield 7
8.0%). Physical properties could not be measured because the product was unstable.

[0045]

Example 6 Examples 6 to 9 below show a hydrogen transfer type asymmetric reduction reaction using isopropyl alcohol as a hydrogen source. Under an argon atmosphere, 36.6 mg (0.05 mmol) of Cp ^* Ir ((S, S) -TsDPEN) Cl was placed in Schlenk. A mixed solution of 600 mg (5.0 mmol) of acetophenone, 49.5 ml of isopropyl alcohol and 0.5 ml (0.05 mmol) of a 0.1M potassium hydroxide isopropyl alcohol solution was added dropwise by a cannula, and the mixture was reacted at room temperature for 24 hours.
After completion of the reaction, the mixture was neutralized with 1.0 N hydrochloric acid, and the solvent was distilled off under reduced pressure. Distilled water was added to the residue, and extraction was performed with ethyl acetate.
The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the target product (S) -1-phenyl was subjected to column chromatography (silica gel, n-hexane: ethyl acetate = 4: 1). Ethanol was isolated and purified (
240 mg, yield 40%). 90% as determined by HPLC
ee (Daicel Chiralcel OD).

[0046]

[Example 7] Cp ^* Rh in Schlenk under argon atmosphere
((S, S) -TsDPEN) Cl 32 mg (0.05 mmol) was added. A mixed solution of 600 mg (5.0 mmol) of acetophenone, 49.5 ml of isopropyl alcohol and 0.5 ml (0.05 mmol) of 0.1 M potassium hydroxide isopropyl alcohol solution was added dropwise to the solution with a cannula, and the mixture was reacted at room temperature for 24 hours. After the reaction,
The mixture was neutralized with 1.0 N hydrochloric acid, and the solvent was distilled off under reduced pressure. Distilled water was added to the residue, and extraction was performed with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the product was purified by column chromatography (silica gel, n-hexane: ethyl acetate = 4: 1).
(S) -1-phenylethanol was isolated and purified (410 mg, yield
68%). As measured by HPLC, 92% ee (Daicel C
hiralcel OD)

[0047]

[Embodiment 8] Cp ^* Ir in Schlenk under argon atmosphere
36.6 mg (0.05 mmol) of ((S, S) -TsDPEN) Cl was added. A mixed solution of 730 mg (5.0 mmol) of 1-tetralone, 49.5 ml of isopropyl alcohol, and 0.5 ml (0.05 mmol) of a 0.1 M potassium hydroxide isopropyl alcohol solution was dropped with a cannula, and reacted at 45 ° C. for 48 hours. After the reaction,
The mixture was neutralized with 1.0 N hydrochloric acid, and the solvent was distilled off under reduced pressure. Distilled water was added to the residue, and extraction was performed with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the product was purified by column chromatography (silica gel, n-hexane: ethyl acetate = 4: 1).
(S) -1-tetralol was isolated and purified (296 mg, yield 40
%). As measured by HPLC, 94% ee (Daicel Chi
ralcel OD).

[0048]

Example 9 Cp ^* Rh in Schlenk under argon atmosphere
((S, S) -TsDPEN) Cl 32 mg (0.05 mmol) was added. to this
A mixed solution of 730 mg (5.0 mmol) of 1-tetralone, 49.5 ml of isopropyl alcohol, and 0.5 ml (0.05 mmol) of a 0.1 M potassium hydroxide isopropyl alcohol solution was dropped with a cannula, and the mixture was reacted at room temperature for 24 hours. After the reaction, 1.
The mixture was neutralized with 0 N hydrochloric acid, and the solvent was distilled off under reduced pressure. Distilled water was added to the residue, and extraction was performed with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and column chromatography (silica gel,
n-Hexane: ethyl acetate = 4: 1) to give the desired product (S) -1-
Tetralol was isolated and purified (266 mg, yield 36%). HPLC
97% ee (Daicel Chiralcel OD)
Met.

[0049]

Industrial Applicability The present invention provides a novel transition metal complex that can be industrially used as a catalyst for a hydrogen transfer type reduction reaction. When the optically active transition metal complex of the present invention is used, for example, for the synthesis of an optically active alcohol from an aromatic ketone, unlike hydrogen gas as a hydrogen source, there is no need for a pressure-resistant reactor, and excellent operation is possible. Safety and safety, and
Optically active alcohols can be synthesized with high selectivity.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 35/36 C07C 35/36 C07F 15/00 C07F 15/00 EB 15/06 15/06 // C07B 61/00 300 C07B 61/00 300 C07M 7:00

Claims (5)

[Claims] 1. The following general formula (1): (Wherein R is hydrogen, a methyl group or two adjacent R may be bonded together to form a 6-membered heterocyclic ring. M is Rh, I
R represents Co, R ¹ represents a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group, a naphthalenesulfonyl group, a camphorsulfonyl group, and R ² represents a cyclohexyl group,
A phenyl group, a phenyl group which may have a substituent, and a naphthyl group are each shown, or R ² may form a cyclohexane ring. The transition metal complex represented by). 2. The following general formula (2) produced by treating the general formula (1) with a base: (Wherein, R ¹ , M, R ¹ and R ² have the above-mentioned meanings). 3. The following general formula (3) produced by treating general formula (2) in isopropanol: (Wherein, R ¹ , M, R ¹ and R ² have the above-mentioned meanings). 4. The following general formula (4): (Wherein, R ³ represents a hydrogen atom, a lower alkyl group, R ⁴ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, an amino group, a dimethylamino group, a carboxyl group,
R ⁴ represents a lower alkoxycarbonyl group or a nitro group, and when R ⁴ is in the ortho position, R ³ and R ⁴ may form a 5-, 6-, or 7-membered cyclo ring. ) Represents an aromatic ketone represented by
Asymmetric hydrogenation reaction by a hydrogen transfer type reduction reaction in the presence of the transition metal complex represented by the formula (1), the formula (2) or the formula (3) according to claim 1 to claim 3. Equation (5), (Wherein, R ³ and R ⁴ have the same meanings as described above). 5. The method for producing an optically active alcohol according to claim 4, wherein formic acid, formate or formate or an alcohol compound is used as the hydrogen supply compound for the hydrogen transfer type reduction reaction.