JP2903737B2 - Optically active biferrocene derivatives, intermediates thereof and methods for producing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound of the formula [I] (Wherein, Ar represents an aryl group, X represents (CHR ¹ ) _n , n represents a numerical value of 0 to ¹ , and R ¹ represents a lower alkyl group.)

The intermediate of formula [II] (Wherein, Ar, X, n and R ¹ have the same meanings as described above) and a method for producing the same.

[0003]

2. Description of the Related Art Various types of biferrocene derivatives have been conventionally known. For example, biferrocene derivatives substituted with an alkyl group, an aminoalkyl group, a carbonyl group and the like are known (for example, Tetrahedron, 26 , 5453 (1970), Monatsh Chem., 100,
1515 (1969), J. Organometal Chem., 35 , 351 (1972), J. Or
ganometal Chem., 67 , 407 (1974) etc.). However, no phosphorus-containing biferrocene derivative is known at all. The present inventors have synthesized various phosphorus-containing biferrocene derivatives, and as a result of intensive studies, have found that the phosphorus-containing optically active biferrocene derivative [I] of the present invention can be coordinated by an asymmetric synthesis reaction. The present invention was found to be useful as a child, and the present invention was completed through further various studies.

[0004]

That is, the present invention provides a compound of the formula [I] (Wherein, Ar represents an aryl group, X represents (CHR ¹ ) _n , n represents a numerical value of 0 to ¹ , and R ¹ represents a lower alkyl group.)

The intermediate [II] (Wherein, Ar, X, n, and R ¹ have the same meanings as described above.)
And optically active biphosphinyl ferrocene represented by the formula:

Next, the present invention will be described in more detail. The optically active biferrocene derivative [I] of the present invention can be produced, for example, by reducing optically active biphosphinyl ferrocene [II]. Examples of the reducing agent include lithium aluminum hydride, hexachlorodisilane, trichlorosilane and trialkylamine, but lithium aluminum hydride is preferably used. The amount of the reducing agent used is usually based on the optically active biphosphinyl ferrocene [II].
0.5 to 5 equivalents.

[0007] The reduction reaction is usually carried out in the presence of a solvent. Examples of such a solvent include carboxylate esters such as ethyl acetate, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, ethers such as tetrahydrofuran, and halogenated hydrocarbons such as chloroform. It is an aromatic hydrocarbon. The solvent is optically active biphosphinyl ferrocene (I
It is usually used in an amount of 1 to 100 times the weight of [I]. The reaction temperature is usually from 0 to 150 ° C., and the reaction is usually completed in about 1 to 50 hours.

After completion of the reaction, the optically active biferrocene derivative [I] can be obtained by removing inorganic substances derived from the reducing agent by a conventional method. It can be further improved in optical and chemical purity by means such as column chromatography and recrystallization.

Thus, the optically active biferrocene derivative represented by the formula [I], which is the object of the present invention, is obtained.
As r, for example, phenyl, O-, m-, P-tolyl, O-, m-,
P-ethylphenyl, O-, m-, P-methoxyphenyl, O-, m-,
And aryl groups such as P-trifluoromethylphenyl and O-, m-, P-trifluoromethoxyphenyl. Also X
The mere bond, R ₁ is, for example, methyl, ethyl, propyl, R ₁ substituted methylene group is a lower alkyl group-butyl and the like.

As more specific compounds, for example, 2,2 ^"
-Bis (diphenylphosphino) -1,1 ^" -biferrocene, 2,2 ^" -bis [di (p-tolyl) phosphino] -1,1 ^"
-Biferrocene, 2,2 ^" -bis [di (p-methoxyphenyl) phosphino] -1,1 ^" -biferrocene, 2,2 ^" -bis [di (p-trifluoromethylphenyl) phosphino]-
1,1 ^" -biferrocene, 2,2 ^" -bis [di (P-trifluoromethoxyphenyl) phosphino] -1,1 ^" -biferrocene, 2,2 ^" -bis [1- (diphenyl) phosphino) ethyl]- 1,1 ^" -biferrocene, 2,2 ^" -bis [1- (di-P-
Tolylphosphino) ethyl] -1,1 ^" -biferrocene, 2,2
^" -Bis [1- [di (P-trifluoromethylphenyl) phosphino] ethyl] -1,1 ^" -biferrocene, 2,2 ^" -bis [1- [di (P-trifluoromethoxyphenyl) phosphino] ethyl] -1,1 ^" -biferrocene and 2,2 ^" -bis [1- (diphenylphosphino) propyl] -1,1 ^" -biferrocene.

The optically active biferrocene derivative [I] of the present invention is useful as a ligand in organic synthesis reactions, particularly in asymmetric synthesis reactions, and those coordinated to metal compounds such as palladium complexes and platinum complexes are useful. , Especially asymmetric hydrogenation,
It is useful as an asymmetric catalyst such as asymmetric cross coupling, asymmetric allylation, and asymmetric aldol condensation.

Next, the optically active biferrocene derivative [I]
Optically active biphosphinyl ferrocene [I
I] will be described. N in the formula [II]
Is 0, that is, when X is a mere bond, it can be produced, for example, by the following route.

[0013]

That is, (1) ferrocene is reacted with diarylphosphinyl chloride in the presence of a base to obtain diarylphosphinyl ferrocene [III]. Examples of the diarylphosphinyl chloride include diphenylphosphinyl chloride, di (p-tolyl) phosphinyl chloride, di (P-methoxyphenyl) phosphinyl chloride and the like. As the base, t-butyllithium is usually used. Compound [III] can also be produced according to a known method, for example, the method described in J. Org. Chem., 28 , 1090 (1963).

(2) Next, a strong base is reacted with the compound [III], and then with a halogen to obtain dl-halogenoferocenylphosphine oxide [IV]. The reaction is
It is usually performed in the presence of a solvent. Such solvents include:
Aprotic solvents, for example, ether solvents such as tetrahydrofuran, dimethoxyethane, 1,4-dioxane and diethyl ether are preferably used.

The strong base used herein includes, for example, organic lithium reagents such as lithium isopropylamide, n-butyllithium and t-butyllithium, and organic magnesium reagents such as bromodiisopropylmagnesium amide. When an organomagnesium reagent is used, halogen is preferably introduced into the ferrocene group instead of the phenyl group, and moreover into the ortho-position of the phosphinyl group substituted by the ferrocene group. The strong base is usually 1 to compound [III].
Used 5 mole times.

As the halogens, iodine, bromine and the like are usually used, and the amount of use is usually 1 to 10 moles per mole of the compound [III]. Reaction temperature is usually -78 ° C
To room temperature, preferably from 0 ° C to room temperature. Dl obtained
Halogenoferrocenyl phosphine oxide (IV) is
Purification can also be performed by purification means such as distillation, recrystallization, and various types of chromatography.

(3) Then, the compound [IV] is homocoupled in the presence of a metal catalyst to obtain dl biphosphinyl ferrocene [V]. The reaction is usually carried out after thoroughly mixing the compound [IV] and the metal catalyst, and then sealing in an atmosphere of an inert gas such as nitrogen or argon. Examples of the metal catalyst include copper powder, nickel powder, nickel complex-aluminum catalyst such as nickel acetylacetonate-diisobutylaluminum hydride, and nickel carbonyl-zinc catalyst. When a nickel complex-aluminum catalyst is used, it is preferable to use the catalyst because the system becomes uniform and the reaction proceeds smoothly. The amount of the metal catalyst to be used is generally in the range of 1 to 100 molar times, relative to compound [IV]. The reaction temperature is usually from room temperature to 300 ° C, preferably from room temperature to 100 ° C. The reaction time is usually about 1 to 24 hours.

Thus, dl-biphosphinyl ferrocene [V] is obtained, but almost no meso form is formed, and the dl form is selectively obtained. The obtained dl-biphosphinyl ferrocene [V] can be purified by purification means such as distillation, recrystallization, and various types of chromatography.

(4) Next, the dl form of the compound [V] is optically resolved using an optically active organic acid, whereby an optically active biphosphinyl ferrocene can be produced.
Optical resolution is usually performed in the presence of a solvent. Such solvents include, for example, ester solvents such as ethyl acetate,
Examples include aromatic solvents such as benzene and toluene, ether solvents such as tetrahydrofuran, alcohol solvents such as methanol and ethanol, and halogenated hydrocarbon solvents such as methylene chloride and chloroform.

Examples of the optically active organic acid include tartaric acid derivatives such as benzoyltartaric acid and camphorsulfonic acid. Such an organic acid is a compound [V] dl
It is usually used in an amount of 0.5 to 1 times the body. The obtained optically active biphosphinyl ferrocene can be further purified by a purification means such as recrystallization.

On the other hand, when n in the optically active biphosphinyl ferrocene [II] is 1, that is, X is CHR ¹ , it can be produced, for example, by the following route.

For example, (5) a strong base is reacted with an optically active ferrocenylamine [VI], and then reacted with a halogen to obtain an optically active halogenoferrocenylamine [VII].
To manufacture. Examples of R ¹ in the compound [VI] include the same lower alkyl groups as described above, such as methyl, ethyl, propyl, and butyl. R ² includes, for example, the same lower alkyl group as R ¹ . Such compounds are described, for example, in J. Am. Chem. Soc., 92 , 5389 (1
970). The reaction is usually performed in the presence of a solvent. Examples of such a solvent include the same solvents as described in the above step (2).

As the strong base, for example,
The same organic lithium reagent and organic magnesium reagent as described in (2) can be used. When an organomagnesium reagent is used, it is preferable to use it because a halogen is selectively introduced into the ortho position of the phosphine group. The strong base is used usually in an amount of 1 to 5 moles compared to the compound [VI].

As the halogens, iodine, bromine and the like are usually used, and the amount of use is usually 1 to 10 moles per mole of the compound [VI]. Reaction temperature is usually -78 ° C
To room temperature, preferably from 0 ° C to room temperature. The obtained optically active halogenoferocenylamine [VII] is distilled,
It can also be purified by purification means such as recrystallization and various types of chromatography.

(6) Then, after reacting the compound [VII] with an alkyl halide and then reacting it with a diarylphosphine oxide, or by reacting a diarylphosphine in place of the diarylphosphine oxide and further oxidizing it, An active halogenoferrocenyl phosphine oxide [VIII] is produced.
The reaction is usually performed in the presence of a solvent. Examples of such a solvent include ketone solvents such as acetone and methyl ethyl ketone, aromatic solvents such as benzene and toluene, ether solvents such as tetrahydrofuran and diethyl ether, and nitrile solvents such as acetonitrile. The amount to be used is generally 1 to 50 with respect to compound [VII].
Weight times.

As the alkyl halide, methyl iodide, ethyl iodide and the like are usually used.
It is usually 1 to 10 moles compared to Compound [VII].
The reaction is usually carried out in the range from room temperature to the boiling point of the solvent. Examples of the diaryl phosphine oxide include diphenyl phosphine oxide, di (p-tolyl) phosphine oxide, di (p-methoxyphenyl) phosphine oxide and the like. It is 10 mole times.

Examples of the diarylphosphine include diphenylphosphine, di (p-tolyl) phosphine,
Di (p-methoxyphenyl) phosphine and the like are used, and the amount of use is usually 1 to 10 moles compared to Compound [VII]. The reaction of the phosphorus compound is usually carried out in the range from room temperature to the boiling point of the solvent. In oxidizing, a peroxide such as hydrogen peroxide is usually used. The amount of use is usually 1 to 10 moles per mole of Compound [VII]. The oxidation is usually carried out at a temperature in the range of -50C to room temperature.

The obtained optically active halogenoferrocenyl phosphine oxide [VIII] can be purified by purification means such as distillation, recrystallization and various types of chromatography.

(7) Next, an optically active biphosphinyl ferrocene is produced by homocoupling the compound [VIII] in the presence of a metal catalyst. The reaction is usually carried out after thoroughly mixing the compound [VIII] and the metal catalyst, and then sealing in an atmosphere of an inert gas such as nitrogen or argon. As the metal catalyst, for example, copper powder, nickel powder,
Examples include nickel complex-aluminum catalysts such as nickel acetylacetonate-dibutylaluminum hydride, and nickel carbonyl-zinc catalysts. When a nickel complex-aluminum catalyst is used, it is preferable to use the catalyst because the system becomes uniform and the reaction proceeds smoothly. The amount of the metal catalyst to be used is generally in a range of 1 to 100 moles per mole of the compound [VIII].

The reaction temperature is usually between room temperature and 300 ° C., preferably between room temperature and 100 ° C. The reaction time is usually about 1 to 24 hours. The obtained optically active biphosphinyl ferrocene can be purified by purification means such as distillation, recrystallization, and various types of chromatography.

[0032]

The optically active biferrocene derivative [I] of the present invention is useful as a ligand in an organic synthesis reaction, particularly in an asymmetric synthesis reaction, and is a compound coordinated to a metal compound such as a palladium complex or a platinum complex. Etc. are, inter alia, asymmetric hydrogenation,
It is useful as an asymmetric catalyst such as asymmetric cross coupling, asymmetric allylation, and asymmetric aldol condensation. Further, according to the production method of the present invention, the optically active biferrocene derivative [I]
Can be manufactured efficiently.

[0033]

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

Example 1 Production Example of Optically Active Biphosphinyl Ferrocene (1) Production of (Diphenylphosphinyl) ferrocene [III] In a 500 ml flask, 39.5 g (212 mmol) of ferrocene was charged, and after purging with argon, nitrogen was added. Under an air stream, 215 ml of dry tetrahydrofuran (THF) was added thereto, followed by stirring. Then, the mixture was cooled to 0 ° C., and t-butyllithium (f: 1.70,
110 ml (187 mmol) of n-pentane solution) was slowly added dropwise, and stirring was continued at the same temperature for 15 minutes and at room temperature for 1 hour.

Dry THF until the deposited orange precipitate dissolves
Was added dropwise to a solution consisting of 4.6 g (194 mmol) of diphenylphosphinyl chloride and 15 ml of dry THF at 0 ° C. over about 2 hours under a nitrogen stream, and at room temperature for 2 hours at room temperature. For 1 hour. Then, a saturated aqueous sodium hydrogen carbonate solution was added thereto, and the mixture was extracted with diethyl ether and methylene chloride.The extract was washed with saturated saline, dried over magnesium sulfate, evaporated, and then treated with an alumina column to give 39.6 g. [III] was obtained.

(2) Production of dl-2-diphenylphosphinyl-1-iodoferrocene [IV] 4.55 g of [III] was placed in a flask, and the flask was purged with argon.
Under a nitrogen stream, 150 ml of dry THF was added thereto, followed by stirring.
Then, the mixture was cooled to 0 ° C. and bromodiisopropylmagnesium amide (f: 0.68, THF solution) 67 ml (45.6
(Mmol), slowly added dropwise, then added 50 ml of dry THF,
Stirring was continued at the same temperature for 45 minutes and at room temperature for 2.5 hours.

Then, the mixture was cooled to 0 ° C., added with 22 g of iodine, stirred for 30 minutes, added with saturated aqueous sodium hydrogen carbonate, filtered, extracted with diethyl ether, washed with saturated saline, dried over magnesium sulfate, and dried. The solvent is distilled off, and the residue is treated with a silica gel column (solvent; methylene chloride: ethyl acetate =
1: 5-methylene chloride: ethyl acetate: methanol = 2:
7: 1) to give 4.52 g of [IV]. This was recrystallized from ethyl acetate to obtain 3.47 g of a purified product. It decomposes at 185 ° C.

(3) Preparation of dl-2,2 ^" -bis (diphenylphosphinyl) -1,1 ^" -biferrocene [V] 1.24 g of [IV] and copper bronze 27.3 activated by a conventional method
g was ground in a mortar and mixed well. The mixture was placed in a test tube, replaced with argon, attached with a ball stopper, and heated at 130 ° C. for 13.5 hours.

After cooling to room temperature, methylene chloride was added for washing and filtration. The solvent was distilled off, and the residue was treated with a silica gel column (solvent; benzene: ethyl acetate = 1: 1 to ethyl acetate) to obtain 0.4 g of a solvent. [V]. This was recrystallized from ethyl acetate to obtain 0.18 g of a purified product.
It decomposes at 270 ° C.

(4) Production of optically active 2,2 ^" -bis (diphenylphosphinyl) -1,1 ^" -biferrocene [IIa] 0.396 g of [V] was dissolved in 150 ml of ethyl acetate, and After a solution of 184.2 mg of-)-dibenzoyltartaric acid (DBTA) and 10 ml of ethyl acetate was added, the solvent was distilled off until the volume became about 80 ml. This was allowed to stand at room temperature, and the generated crystals were separated by filtration to obtain (+)-[IIa] · (−)-DB
0.1753 g of TA was obtained. [Α] _D ²⁰ = + 285.3 ° (C = 1.03, chloroform)

This was recrystallized from ethyl acetate to obtain 0.1313 g. [Α] _D ²⁰ = +294.6 ° (C = 0.7
44, Chloroform) A part of this was treated with 0.75 N caustic soda to give (+)-[IIa] quantitatively. [Α] _D ²⁰ = + 466.8 ° (C = 0.259, chloroform) The remaining (+)-[IIa] · (−)-DBTA 0.1013 g was further recrystallized from ethyl acetate to give 78.2 mg of (+). -[IIa] ・ 1/2
(−)-DBTA was obtained. [Α] _D ²⁰ = + 384.3 ° (C = 0.
This was treated with 0.75N caustic soda to obtain 63.1 mg of (+)-[IIa]. (Α) _D
²⁰ = +522.7 ° (C = 0.445, chloroform)
From the filtrate obtained by filtering the above crystals using (+)-DBTA, (−)
-[IIa] 0.1811 g was obtained. [Α] _D ²⁰ = -515.7 ° (C =
(0.445 Chloroform)

Example 2 Production Example of Optically Active Biphosphinyl Ferrocene (1) (R) -N, N-dimethyl-1-[(S) -2-iodoferrocenyl]
Preparation of ethylamine [VII] At room temperature, a solution consisting of 9.44 g of (R) -N, N-dimethyl-1-[(S) -ferrocenyl] ethylamine and 60 ml of ether
After adding 28 ml of an M n-butyllithium hexane solution and stirring for 2 hours, the mixture was cooled to -30 °, 1.13 g of iodine was added, and the temperature was raised to room temperature while stirring for 1 hour.

Then, the mixture is cooled on ice, an aqueous solution of sodium carbonate is added, and the mixture is extracted with ether. 8.5% for organic layer
Phosphoric acid aqueous solution was added to extract the aqueous layer, sodium carbonate powder was carefully added to the water tank to neutralize, the released oil was extracted with ether, dried over potassium carbonate, evaporated, and distilled under reduced pressure to give 6.12. g of [VII] was obtained. It has the diastereomer (R) -N, N-dimethyl in addition to [VII]
It contained -1-[(R) -2-iodoferrocenyl] ethylamine and its ratio was about 1/10. Boiling point: 143 to 144 ° C / 0.2mmHg g

(2) Preparation of (S) -2-[(R) -1- (diphenylphosphinyl) ethyl] -1-iodoferrocene [VIII] 6.1 A solution consisting of 12 g of [VII] and 50 ml of acetone , 23g
And the mixture was stirred at room temperature for 1 hour. A yellow precipitate formed. After ether was added to completely precipitate the product, the mixture was filtered, washed and dried. Then, change this to 14
After suspending in 0 ml of acetonitrile, blowing argon gas into the suspension, 10.7 g of diphenylphosphine was added thereto.
React at 12 ° C for 12 hours.

Then, after acetonitrile was distilled off, methylene chloride was added, the ammonium salt was removed by filtration, and the mixture was heated to 100 ° C. under reduced pressure (0.7 mmHg) to remove excess diphenylphosphine. The residue was dissolved in 100 ml of acetone, cooled to -20 ° C, 6 ml of 30% hydrogen peroxide was added and stirred for 30 minutes. After carefully adding an aqueous solution of sodium thiosulfate, extraction with methylene chloride, drying with magnesium sulfate, evaporation of the solvent, and treatment with an alumina column (solvent: ethyl acetate) gave 2.32 g of [VIII]. [Α] _D ²⁵ = + 18 ° (C = 0.5, chloroform) Mass spec (as C ₂₄ H ₂₂ OPFe) Measured 539.9793 Calculated 539.9800

(3) Preparation of (S, S) -2,2 ^" -bis [(R) -1- (diphenylphosphinyl) ethyl] biferrocene [IIb] 1.76 g of [VIII] and activated copper The powder was mixed with 2.1 g of powder and heated for 21 hours under an argon atmosphere at 130 ° C. After cooling to room temperature, methylene chloride was added and the mixture was filtered, the solvent was distilled off from the filtrate, and the mixture was treated with a silica gel column (solvent: benzene). :
Ethyl acetate = 1: 1) gave 447 mg of [IIb]
I got Mp 245 to 250 DEG ° C. (decomposition) Elemental analysis (C ₄₈ as _{H 44 O 2 P 2 Fe 2} ) Found C 70.02% H 5.39% Calculated C 69.75% H 5.37% [α] _D ²⁵ = -124 ° ( (C = 0.72, chloroform)

Example 3 Production Example of Optically Active Biferrocene (-)-2,2 ^" -bis (diphenylphosphino) -1,1 ^" -
Production of Biferrocene [Ia] 0.18 of (−)-[IIa] obtained in (4) of Example 1 was placed in a flask.
After adding 11 g and replacing with argon, 7 ml of dry xylene, 0.43 ml of trichlorosilane and 0.63 ml of triethylamine were added thereto under a nitrogen stream, and the mixture was heated at 100 ° C. for 0.5 hour, at 120 ° C. for 1 hour, and at reflux temperature for 3 hours. After cooling to room temperature, 1 ml of dry xylene, 0.43 ml of trichlorosilane and 0.63 ml of triethylamine were added, and the mixture was heated again at the reflux temperature for 2 hours. Then, cool to room temperature and trichlorosilane 0.4
3 ml and 0.63 ml of triethylamine are added and the mixture is refluxed at 6
The operation of heating for three hours was repeated three times.

Next, the mixture was cooled to room temperature, a 30% aqueous solution of sodium hydroxide was added, and the mixture was stirred at 60 ° C. for 1 hour, extracted with methylene chloride, dried over magnesium sulfate, evaporated, and treated with a silica gel column (methylene chloride to acetic acid). Ethyl) gave 133 mg of [Ia]. This was dissolved in methylene chloride, reprecipitated by adding n-hexane, and recrystallized from ethanol to obtain 50 mg of a purified product. Mp 226 ° C. [α] ^{_{D 20 = -156 ° (C =}} 0.194, chloroform)

Example 4 Production Example of Optically Active Biferrocene Preparation of (S, S) -2,2 ^" -bis [(R) -1- (diphenylphosphino) ethyl] biferrocene [Ib] 82.7 mg of [IIb] obtained in) and 5 ml of xylene
Was added, and 109 mg of triethylamine and 133 mg of trichlorosilane were added, stirred at 130 ° C. for 6 hours, and cooled to room temperature. Then, add 1.4 ml of 30% aqueous sodium hydroxide solution, stir at 60 ° C for 30 minutes, extract with ether, wash the organic layer with water, dry with sodium sulfate, evaporate the solvent, and treat with an alumina column (solvent: benzene). 35.8mg
[Ib] was obtained.

[Α] _D ²⁵ = −303 ° (C = 0.49, chloroform) ¹ H NMR (CDCl ₃ , 200 MHz) δ 1.35 (m, 6H), 3.49 (q, J = 7.0 Hz, 2H), 3.79 ( m, 2H), 4.12
(m, 2H), 4.30 (s, 10H), 4.55 (m, 2H), 7.1-7.3 (m, 20H) ³¹ P NMR (CDCl ₃ , 81MHz) δ 2.19

Reference Example 1 Production Example of transpalladium complex At room temperature, 14 mg of dichlorobis (acetonitrile) palladium (II) and 42.9 mg of [Ib] obtained in Example 4 were mixed in chloroform, followed by silica gel column treatment (solvent). ;
Methylene chloride) to separate the orange component, which is recrystallized from a mixed solvent of methylene chloride and ether,
The transpalladium complex was obtained with a yield of about 30%. Mp 230 to 235 ° C. (decomposition) Elemental analysis (C ₄₈ H ₄₄ P ₂ Cl as ₂ Fe ₂ Pd) Found C 59.10% H 4.54% Calculated C 59.32% H 4.56%

[0052] _{^{1 H NMR (CDCl 3, 200MHz}} ) δ 1.65 (td, | 3 J PH + 5 J PH | = 13.0 and | 3 J HH |
= 6.6Hz, 6H), 3.72 (m, 2H), 4.8 (m, 2H), 4.31 (s, 10H), 4.40
(m, 2H), 4.67 ( m, 2H), 7.2-7.4 (m, 16H), 7.9-8.0 (m, 4H), 13 C NMR (CDCl 3, 50MHz) δ 19.88, 30.90 (t, | 2 J _PC + ⁴ J _PC | = 18Hz), 67.61,6
8.06,70.14 (Cp), 72.74,86.68,91.71 (t, | ² J _PC + ⁴ J
_{PC | = 10Hz), 127.08 (} t, | 3 J PC + 5 J PC | = 9Hz, met
a), 127.23 (t, | 3 J PC + 5 J PC | = 7Hz, meta), 127.93
(t, │ ¹ J _PC + ³ J _PC │ = 38Hz, ipso), 129.12 (para), 13
0.59 (para), 130.94 (t, │ ¹ J _PC ＋ ³ J _PC │ = 43Hz, ips
o), 133.46 (t, | ² J _PC + ⁴ J _PC | = 9 Hz, ortho), 137.80
(t, | ² J _PC + ⁴ J _PC | = 11 Hz, ortho), ³¹ P NMR (CDCl ₃ , 81 MHz) δ 25.11

Reference Example 2 Production Example of transplatinum complex At room temperature, 24.5 mg of transdichlorobis (acetonitrile) platinum (II) and 55.6 mg of [Ib] obtained in Example 4 were mixed in chloroform, and then mixed at 40 ° C. And react for 12 hours.
A mixture of trans and cis isomers (about 20: 1) was obtained. The mixture was treated with a silica gel column (solvent: dichloromethane), and the orange component flowing out was collected and recrystallized from a mixed solvent of dichloromethane and ether to obtain a trans-platinum complex in a yield of about 30%. A cis-platinum complex was obtained from the orange component component that subsequently flowed out.

[0054] "trans platinum complex" melting point 240 to 245 ° C. (decomposition) Elemental analysis (C ₄₈ H ₄₄ P ₂ Cl as ₂ Fe ₂ Pt) Found C 54.06% H 4.04% Calculated C 54.36% H 4.18% ¹ _{H NMR (CDCl 3, 200MHz)} δ 1.66 (td, | 3 J PH + 5 J PH | = 12.2 and | 3 J HH |
= 6.6Hz, 6H), 3.76 (m, 2H), 4.06 (m, | ² J _PH + ⁴ J _PH | =
4.0Hz, 2H), 4.31 (s, 10H), 4.39 (m, 2H), 4.64 (m, 2H), 7.2-7.
4 (m, 16H), 7.8-7.9 (m, 4H), 13 C NMR (CDCl 3, 50MHz) δ 19.98, 30.90 (t, | 3 J 195Pt-C | = 22Hz), 30.85 (quin
t, │ ¹ J _PC + ³ J _PC │ = 27Hz), 67.10, 67.85, 69.71 (Cp),
72.55, 86.63, 91.62 (t, │ ³ J _PC + ⁵ J _PC │ = 8Hz), 126.9
7 (t, │ ¹ J _PC + ³ J _PC │ = 46Hz, ipso), 127.05 (t, │ ^{3
_{J PC + 5 J PC | =}} 10Hz, meta), 127.24 (t, | 3 J PC + 5 J
_PC | = 9Hz, imeta), 129.19 (para), 129.90 (t, | ¹ J _PC +
³ J _PC | = 50Hz, ipso), 130.60 (para), 133.48 (t, | ² J _{PC
^{+ 4 J PC | = 9Hz,}} ortho), 137.53 (t, | 2 J PC + 4 J PC | =
^{11Hz, ortho), 31 P NMR} (CDCl 3, 81MHz) δ 21.41 (t, J 195Pt-P = 2612Hz)

"Cis platinum complex" ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.7-016 (m, 6H), 3.74 (m, 2H), 3.88 (s, 10H), 4.42 (m, 2
H), 4.87 (m, 2H), 7.2-7.4 (m, 12H), 7.5-7.6 (m, 4H), 7.9-8.0
(m, 4H) J ³¹ P NMR (CDCl ₃ , _81MHz ) δ 16.12 (t, J _195Pt-P = 3668Hz)

REFERENCE EXAMPLE 3 Production Example of Palladium Complex At room temperature, about 4 ml of methylene chloride was obtained in Example 3 [I
a] 24.8 mg and 8.71 mg of dichlorobis (acetonitrile) palladium (II) were added, and the mixture was stirred for 30 minutes. Then, diethyl ether was added thereto little by little to precipitate purple crystals. 28 mg of the palladium complex were obtained.

[Α] _D ²⁰ = −712.3 ° (C = 0.334, methylene chloride) ¹ H NMR (CDCl ₃ , 200 MHz) δ 3.66 (s, 2H), 3.70 (br-s, 10H), 4.47 (t, J = 2.5Hz, 2H), 4.
84 to 4.87 (m, 2H), 7.38 to 7.65 (m, 12H), 7.65 to 7.87 (br, 4
H), 8.13~8.41 (br, 4H ) 13 C NMR (CDCl 3, 50MHz) δ 70.41 (t, J = 3.4), 71.33 (s), 73.20~74.80 (br-m), 77.7
0 to 78.55 (br-m), 86.40 to 86.85 (m), 127.33 to 127.85
(m), 128.52-129.10 (m), 130.59 (s), 132.24 (s), 133.30
~133.96 (m), 136.70 (s ) 31 P NMR (CDCl 3, 81MHz) δ 24.00~29.00 (br)

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C07F 17/02 B01J 23/72 C07B 61/00 300 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] 1. The formula [I] (Wherein, Ar represents an aryl group, X represents (CHR ¹ ) _n , n represents a numerical value of 0 to ¹ , and R ¹ represents a lower alkyl group). 2. The formula [II] (Wherein, Ar represents an aryl group, X represents (CHR ¹ ) _n , n represents a numerical value of 0 to ¹ , and R ¹ represents a lower alkyl group.) 2. A method for producing an optically active biferrocene derivative represented by the formula [I] according to claim 1, wherein the reduction is carried out. 3. An optically active biphosphinyl ferrocene represented by the formula [II] according to claim 2. 4. The optically active biphosphinyl ferrocene according to claim 3, wherein n is 0. 5. The formula [III] (Where Ar represents an aryl group), a strong base is allowed to act on the phosphinyl ferrocene represented by the formula (IV), (Wherein, Ar has the same meaning as described above, and Y represents a halogen atom.) A dl-halogenoferocenylphosphine oxide represented by the following formula is obtained, followed by homocoupling in the presence of a metal catalyst to obtain a compound represented by the formula [V] 5. A dl-form of biphosphinyl ferrocene represented by the formula (wherein, Ar has the same meaning as described above), and this is optically resolved using an optically active organic acid. The method for producing an optically active biphosphinyl ferrocene of the present invention. 6. The optically active biphosphinyl ferrocene according to claim 3, wherein n is 1. 7. The formula [VI] (Wherein R ¹ represents a lower alkyl group, and R ² represents a lower alkyl group). The reaction of an optically active ferrocenylamine represented by the formula [VII] (Wherein, R ¹ and R ² have the same meanings as described above, and Y represents a halogen atom), and are then treated with an alkyl halide and then reacted with a diarylphosphine oxide. Or by reacting a diarylphosphine in place of the diarylphosphine oxide and further oxidizing, to obtain a compound of the formula (VIII) (Wherein, R ¹ and Y have the same meanings as described above, and Ar represents an aryl group.), And then homocoupling in the presence of a metal catalyst. The method for producing an optically active biphosphinyl ferrocene according to claim 6, wherein