JPH04283596A - Optically active biferrocene derivative, intermediate thereof and production thereof - Google Patents

Abstract

PURPOSE:To obtain the new title derivative for ligand of asymmetric synthesis reaction, etc., by reacting a specific phosphinylferrocene with a strong base, then reacting the reaction product with halogen, subjecting the resultant reaction product to homocoupling in the presence of a metal catalyst, subjecting the coupled compound to optical resolution and reducing the resultant optically active compound. CONSTITUTION:Phosphinylferrocene [e.g. diphenylphosphinyl) ferrocene] expressed by formula I (Ar is aryl) is reacted with a strong base and then reacted with halogens to afford dl-halogenoferrocenylphosphineoxide expressed by formula II (Y is halogen), which is then subjected to homocoupling in the presence of a metal catalyst to give dl-biphosphinylferrocene expressed by formula III and the dl-biphosphinylferrocene expressed by formula III is subjected to optical resolution using an optically active organic acid and then reduced to provide the objective optically active biferrocene [e.g. 2,2'-bis(diphenylphosphino)-1,1'-biferrocene].

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to the formula [I] (wherein Ar represents an aryl group, X represents (CHR1)n, and n is 0 to
1, and R1 represents a lower alkyl group. ), an optically active biferrocene derivative represented by

[0002] This invention relates to optically active biphosphinylferrocenes represented by the formula [II] (wherein Ar, be.

0003

BACKGROUND OF THE INVENTION Various biferrocene derivatives have been known. For example, biferrocene derivatives substituted with alkyl groups, aminoalkyl groups, carbonyl groups, etc. are known (for example, Tetrahedron, 26, 5453 (197
0), Monatsh Chem. ,100,151
5 (1969), J. Organometal Che
m. , 35, 351 (1972), J. Organom
etal Chem. , 67, 407 (1974), etc.)
. However, nothing is known about biferrocene derivatives containing phosphorus. The present inventors have synthesized various phosphorus-containing biferrocene derivatives, and as a result of extensive studies, the optically active biferrocene derivative [I] of the present invention containing phosphorus has been found to be suitable for coordination in asymmetric synthesis reactions. In addition to discovering that the present invention is useful as a child, the present invention was completed after further various studies.

0004

[Means for Solving the Problems] That is, the present invention solves the problems by the formula [
I] Optically active biferrocene derivative represented by (wherein, Ar represents an aryl group, X represents (CHR1)n, n represents a numerical value of 0 to 1, and R1 represents a lower alkyl group);

0
[005] Its intermediate is the formula [II] (wherein, Ar, X
, n, R1 represents the same meaning as above. ) and a method for producing them.

Next, the present invention will be explained in more detail. The optically active biferrocene derivative [I] of the present invention can be produced, for example, by reducing optically active biphosphinylferrocene [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 0.5 to 5 equivalents relative to the optically active biphosphinylferrocene [II].

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

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

[0009] In this way, the optically active biferrocene derivative represented by formula [I], which is the object of the present invention, is obtained.
Examples of r include phenyl, O-, m-, P-tolyl, O-, m-, P-ethylphenyl, O-, m-, P-
Examples include aryl groups such as methoxyphenyl, O-, m-, P-trifluoromethylphenyl, O-, m-, P-trifluoromethoxyphenyl. Also, as X,
Examples thereof include a simple bond, an R1-substituted methylene group in which R1 is a lower alkyl group such as methyl, ethyl, propyl, butyl, and the like.

More specific compounds include, 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-(diP-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, 2,2"-bis[1-(diphenylphosphino)propyl]-1,1"-biferrocene, and the like.

Optically active biferrocene derivatives of the present invention [I
] are useful as ligands for organic synthesis reactions, especially asymmetric synthesis reactions, and those coordinated to metal compounds, such as palladium complexes and platinum complexes, are particularly useful for asymmetric hydrogenation and asymmetric cross-coupling. It is useful as an asymmetric catalyst for , asymmetric allylation, asymmetric aldol condensation, etc.

Next, optically active biferrocene derivative [I]
Optically active biphosphinylferrocene [I
The manufacturing method of [I] will be explained. When n in formula [II] is 0, that is, when X is a simple 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,
Diarylphosphinylferrocene [III] is obtained. Examples of diarylphosphinyl chloride include diphenylphosphinyl chloride, di(p-tolyl)
Phosphinyl chloride, di(P-methoxyphenyl)
Examples include phosphinyl chloride. As the base, t-butyllithium is usually used. Compound [III] can also be prepared by known methods such as J. Org.
Chem. , 28, 1090 (1963).

(2) Next, compound [III] is reacted with a strong base and then reacted with a halogen to obtain dl-halogenoferrocenylphosphine oxide [IV]. The reaction is usually carried out in the presence of a solvent. As such a solvent, an aprotic solvent such as an ether solvent such as tetrahydrofuran, dimethoxyethane, 1,4-dioxane, or diethyl ether is preferably used.

Examples of strong bases used here include lithium isopropylamide, n-butyllithium, t
Examples include organolithium reagents such as -butyllithium, organomagnesium reagents such as bromodiisopropylmagnesiumamide, and the like. When an organomagnesium reagent is used, the halogen is selectively introduced into the ferrocene group rather than the phenyl group, and moreover, into the ortho position of the phosphinyl group substituted with the ferrocene group, so it is preferable to use this reagent. The strong base is usually used in an amount of 1 to 5 times the mole of compound [III].

Iodine, bromine, etc. are usually used as the halogens, and the amount used is usually 1 to 10 times the mole of compound [III]. The reaction temperature is usually -78°C to room temperature, preferably 0°C to room temperature. The obtained dl-halogenoferrocenylphosphine oxide [IV] can also be purified by purification means such as distillation, recrystallization, and various chromatography.

(3) Next, by homocoupling compound [IV] in the presence of a metal catalyst, dl
Biphosphinylferrocene [V] is obtained. The reaction is usually carried out by thoroughly mixing compound [IV] and a metal catalyst, and then adding nitrogen,
The test is carried out under a sealed atmosphere of inert gas such as argon. Examples of the metal catalyst include copper powder, nickel powder, nickel complex-aluminum catalysts such as nickel acetylacetonate-diisobutylaluminum hydride, and nickel carbonyl-zinc catalysts. When a nickel complex-aluminum catalyst is used, the system becomes homogeneous and the reaction proceeds smoothly, so it is preferable to use this. The amount of metal catalyst used is usually 1% per compound [IV].
It is in the range of ~100 mole times. The reaction temperature is usually room temperature to 300°C, preferably room temperature to 100°C. The reaction time is usually about 1 to 24 hours.

In this way, dl-biphosphinylferrocene [V] is obtained, but the meso form is hardly produced and the dl form is selectively obtained. The obtained dl-biphosphinylferrocene [V] can also be purified by purification means such as distillation, recrystallization, and various chromatography.

(4) Next, optically active biphosphinylferrocene can be produced by optically resolving the dl form of compound [V] using an optically active organic acid. Optical resolution is usually performed in the presence of a solvent. Examples of such solvents include 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 optically active organic acids include tartaric acid derivatives such as benzoyltartaric acid, camphorsulfonic acid, and the like. Such an organic acid is a compound [V]d
It is usually used in an amount of 0.5 to 1 mole per mol of the l-isomer. The obtained optically active biphosphinylferrocene can be further purified by purification means such as recrystallization.

On the other hand, when n in optically active biphosphinylferrocene [II] is 1, that is, X is CHR1, it can be produced, for example, by the following route.

For example, (5) optically active ferrocenylamine [VI] is reacted with a strong base and then reacted with a halogen to form optically active halogenoferrocenylamine [
VII]. R1 in compound [VI]
Examples thereof include the same lower alkyl groups as mentioned above, such as methyl, ethyl, propyl, and butyl. Also R
Examples of 2 include lower alkyl groups similar to R1. Such compounds are described, for example, in J. A
m. Chem. Soc. , 92, 5389 (
1970). The reaction is usually carried out in the presence of a solvent. Examples of such a solvent include the same solvents as described in step (2) above.

In addition, as a strong base, for example, the above-mentioned step (
Examples include organolithium reagents and organomagnesium reagents similar to those described in 2). When an organomagnesium reagent is used, the halogen is selectively introduced into the ortho position of the phosphine group, so it is preferable to use this reagent. A strong base is usually 1 for compound [VI].
~5 moles are used.

Iodine, bromine, etc. are usually used as halogens, and the amount used is usually 1 to 10 times the mole of compound [VI]. The reaction temperature is usually -
78°C to room temperature, preferably 0°C to room temperature. Obtained optically active halogenoferrocenylamine [VII]
can also be purified by purification means such as distillation, recrystallization, and various types of chromatography.

(6) Next, by reacting compound [VII] with an alkyl halide and then with diarylphosphine oxide, or by reacting diarylphosphine instead of diarylphosphine oxide and further oxidizing, optical Active halogenoferrocenylphosphine oxide [VIII]
Manufacture. The reaction is usually carried out in the presence of a solvent. Examples of such solvents 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 used is usually 1 to 1 for compound [VII].
It is 50 times the weight.

[0027] As the alkyl halide, methyl iodide, ethyl iodide, etc. are usually used, and the amount used is as follows:
The amount is usually 1 to 10 times the mole of compound [VII]. The reaction is usually carried out at a temperature ranging from room temperature to the boiling point of the solvent. Examples of diarylphosphine oxide include diphenylphosphine oxide, di(p-tolyl)
Examples include phosphine oxide, di(p-methoxyphenyl) phosphine oxide, and the amount used is usually 1 to 10 times the mole of compound [VII].

Examples of the diarylphosphine include diphenylphosphine, di(p-tolyl)phosphine, di(p-methoxyphenyl)phosphine, etc., and the amount used is usually 1 to 10% per compound [VII]. 10 moles. The reaction of phosphorus compounds is usually carried out in the range from room temperature to the boiling point of the solvent. For oxidation, peroxides such as hydrogen peroxide are usually used. The amount used is usually 1 to 10 times the mole of compound [VII]. Oxidation is typically carried out at temperatures ranging from -50°C to room temperature.

The obtained optically active halogenoferrocenylphosphine oxide [VIII] can also be purified by purification means such as distillation, recrystallization, and various chromatography.

(7) Next, by homocoupling compound [VIII] in the presence of a metal catalyst,
Produce optically active biphosphinylferrocene. The reaction is usually carried out under a sealed atmosphere of an inert gas such as nitrogen or argon after sufficiently mixing the compound [VIII] and the metal catalyst. Examples of metal catalysts include copper powder, nickel powder, nickel complex-aluminum catalysts such as nickel acetylacetonate-dibutylaluminum hydride,
Examples include nickel carbonyl-zinc catalysts. When a nickel complex-aluminum catalyst is used, the system becomes homogeneous and the reaction proceeds smoothly, so it is preferable to use this. The amount of the metal catalyst used is usually 1 to 100 times the amount of compound [VIII] by mole.

The reaction temperature is usually room temperature to 300°C, preferably room temperature to 100°C. The reaction time is usually 1~
It takes about 24 hours. The obtained optically active biphosphinylferrocene can also be purified by purification means such as distillation, recrystallization, and various chromatography.

[0032]

[Effect of the invention] Optically active biferrocene derivative of the present invention [
I] is useful as a ligand for organic synthesis reactions, especially asymmetric synthesis reactions, and those coordinated to metal compounds, such as palladium complexes and platinum complexes, are particularly useful for asymmetric hydrogenation, asymmetric cross-coupling, etc. It is useful as an asymmetric catalyst for ring, asymmetric allylation, asymmetric aldol condensation, etc. Further, according to the production method of the present invention, optically active biferrocene derivative [I] can be efficiently produced.

[0033]

[Examples] Next, the present invention will be explained in detail based on Examples, but the present invention is not limited to these.

Example 1 Production example (1) of optically active biphosphinylferrocene (
Production of (diphenylphosphinyl) ferrocene [III] 39.5 g of ferrocene (212
After purging with argon, 215 m of dry tetrahydrofuran (THF) was added to the solution under a nitrogen stream.
1 was added and stirred. Next, the mixture was cooled to 0°C, and 110 ml (187 mmol) of t-butyllithium (f: 1.70, n-pentane solution) was slowly added dropwise thereto, followed by stirring at the same temperature for 15 minutes and at room temperature for 1 hour. Ta.

Dry TH until the orange precipitate is dissolved.
After adding F, the solution was mixed with 4.6 g (194 mmol) of diphenylphosphinyl chloride under a nitrogen stream.
and 15 ml of dry THF was added dropwise at 0° C. over about 2 hours, and stirring was continued at the same temperature for 2 hours and at room temperature for 1 hour. Next, saturated sodium bicarbonate solution was added to this, followed by extraction with diethyl ether and methylene chloride, which was washed with saturated brine, dried over magnesium sulfate, the solvent was distilled off, and then treated with an alumina column to obtain 39. 6 g of [III] was obtained.

(2) Production of dl-2-diphenylphosphinyl-1-iodoferrocene [IV] 4.55 g of [III] was placed in a flask, the atmosphere was replaced with argon, and 150 m of dry THF was poured into the flask under a nitrogen stream.
1 was added and stirred. Next, it was cooled to 0°C, and 67 ml (45.6 mmol) of bromodiisopropylmagnesiumamide (f: 0.68, THF solution) was slowly added dropwise under a nitrogen stream, and then 50 ml of dry THF was added, and the mixture was heated at the same temperature for 45 minutes. Stirring was continued for 2.5 hours at room temperature.

[0037] Next, it was cooled to 0°C, and 22g of iodine was added.
After stirring for 30 minutes, add saturated sodium bicarbonate solution, filter, extract with diethyl ether, wash with saturated brine, dry over magnesium sulfate, evaporate the solvent, and then treat with a silica gel column (solvent ; methylene chloride: ethyl acetate = 1:5 ~ methylene chloride: ethyl acetate: methanol = 2:7:1), thereby producing 4.52 g of [IV]
I got it. By recrystallizing this from ethyl acetate, 3.47 g of purified product was obtained. This one is 18
Decomposes at 5°C.

(3) dl-2,2''-bis(diphenylphosphinyl)-1,1''-biferrocene [V
] Production of 1.24 g of [IV] and 27.3 g of copper bronze activated by a conventional method were ground in a mortar and mixed well, placed in a test tube, replaced with argon, fitted with a bead and heated to 130 g. The mixture was heated to 13.5 hours at ℃.

After cooling to room temperature, methylene chloride was added, the mixture was washed, filtered, the solvent was distilled off, and treated with a silica gel column (solvent: benzene:ethyl acetate = 1:1 to ethyl acetate) to give 0.4 g. [V] was obtained.
By recrystallizing this from ethyl acetate, 0.18 g of a purified product was obtained. This substance decomposes at 270°C.

(4) Production of optically active 2,2"-bis(diphenylphosphinyl)-1,1"-biferrocene [IIa] 0.396 g of [V] was converted to 150
ml of ethyl acetate, and to this was added a solution consisting of 184.2 mg of (-)-dibenzoyltartaric acid (DBTA) and 10 ml of ethyl acetate, until the volume was about 80 ml.
The solvent was distilled off to a volume of 1. By leaving this at room temperature and filtering out the formed crystals, (+)-
[IIa] 0.1753 g of (-)-DBTA was obtained. [α] D 20 = +285.3 ° (C = 1.03,
chloroform)

[0041] By recrystallizing this from ethyl acetate, 0.1313 g was obtained. [α]D
20 = +294.6 ° (C = 0.744, chloroform) By treating a part of this with 0.75N caustic soda, quantitatively (+) - [IIa]
I got it. [α]D 20=+466.8° (C=0.259,
chloroform) remaining (+)-[IIa] ・(-)
-DBTA 0.1013g was further recrystallized from ethyl acetate to obtain 78.2mg of (+)-[IIa] ・1
/2 (-)-DBTA was obtained. [α]D 2
0=+384.3° (C=0.49, chloroform) This was treated with 0.75N caustic soda to obtain 63.1 mg of (+)-[IIa]. [α] D 20 = +522.7 ° (C = 0.445
, chloroform) In the same manner, (-)-[IIa
] 0.1811 g was obtained. [α]D20=-51
5.7 ° (C=0.445 chloroform)

Example 2 Production example (1) of optically active biphosphinylferrocene (
Preparation of R)-N,N-dimethyl-1-[(S)-2-iodoferrocenyl] ethylamine [VII] At room temperature, (R)-N,N-dimethyl-1-[(S)
-Ferrocenyl] To a solution consisting of 9.44 g of ethylamine and 60 ml of ether, 28 ml of 1.6M n-butyllithium hexane solution was added and stirred for 2 hours, then cooled to -30°, and 1.13 g of iodine was added.
was added, and the temperature was raised to room temperature while stirring for 1 hour.

[0043] Next, this is ice-cooled, an aqueous sodium carbonate solution is added thereto, and then extracted with ether. 8.5 for organic layer
% phosphoric acid aqueous solution to extract the aqueous layer, carefully add sodium carbonate powder to the water bath to neutralize, extract the liberated oil with ether, dry with potassium carbonate, evaporate the solvent, and distill under reduced pressure. 6.12 g of [VII] was obtained. This product contains the diastereomer (R)-N,N-dimethyl-1-[(R)-2-iodoferrocenyl]ethylamine in addition to [VII], and the ratio is approximately 1/1. There were 10. Boiling point: 143-144℃/0.2mmHg
g

(2) (S)-2-[(R)-1-(
Preparation of ethyl]-1-iodoferrocene [VIII] 6.12 g of [VII]
23 g of methyl iodide was added to a solution consisting of 50 ml of acetone and 50 ml of acetone, and the mixture was stirred at room temperature for 1 hour. A yellow precipitate formed. The product was completely precipitated by adding ether, then filtered, washed and dried. Next, increase this to 140
After suspending the suspension in 1 ml of acetonitrile and blowing argon gas into it, 10.7 g of diphenylphosphine was added and the mixture was reacted at 40°C for 12 hours.

Next, after distilling off acetonitrile, methylene chloride was added, the ammonium salt was removed by filtration, and the mixture was then heated to 100° C. under reduced pressure (0.7 mmHg) to distill off excess diphenylphosphine. The residue was dissolved in 100 ml of acetone and cooled to -20°C, then 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)
By doing so, 2.32 g of [VIII] was obtained. [α]D 25=+18° (C=0.5, chloroform) Mass spectrometry value (as C24H22OPFe) Actual value 539.9793 Calculated value 539.9800

(3) (S,S)-2,2''-bis[(R)-1-(diphenylphosphinyl)ethyl]
Production of biferrocene [IIb] 1.76 g of [V
III] and 2.1 g of activated copper powder were mixed and heated at 130° C. in an argon atmosphere for 21 hours. After cooling to room temperature, methylene chloride was added and filtered, and after distilling off the solvent from the filtrate, it was treated with a silica gel column (solvent;
44 by benzene:ethyl acetate=1:1)
7 mg of [IIb] was obtained. Melting point 245-250℃ (decomposition) Elemental analysis value (
As C48H44O2P2Fe2) Actual value C
70.02% H 5.39% calculated value 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''-biferrocene [Ia] production flask was filled with (-)-[Ia] obtained in Example 1 (4).
After replacing with argon, add 0.1811 g of Ia] and add 7 ml of dry xylene, 0.43 ml of trichlorosilane, and 0.63 ml of triethylamine under a nitrogen stream.
was added and heated at 100°C for 0.5 hours, at 120°C for 1 hour, and at reflux temperature for 3 hours. Cool to room temperature;
1 ml dry xylene, 0.43 ml trichlorosilane
, triethylamine (0.63 ml) was added thereto, and the mixture was heated again at reflux temperature for 2 hours. Next, cool to room temperature and add 0.43 ml of trichlorosilane and triethylamine.
The operation of adding 0.63 ml and heating at reflux temperature for 6 hours was repeated three times.

Next, the mixture was cooled to room temperature, 30% aqueous sodium hydroxide solution was added, and the mixture was stirred at 60°C for 1 hour, extracted with methylene chloride, dried over magnesium sulfate, and the solvent was distilled off.
By treatment with a silica gel column (methylene chloride - ethyl acetate), 133 mg of [Ia] was obtained. After dissolving this in methylene chloride, it was reprecipitated by adding n-hexane, and then recrystallized from ethanol.
0 mg of purified product was obtained. Melting point 226 °C [α]D 20 = -156 ° (C = 0.194, chloroform)

Example 4 Production example of optically active biferrocene (S,S)-2,2''-bis[(R)-1-(diphenylphosphino)ethyl] Production of biferrocene [Ib] Example 2 (3) ) obtained [IIb] 82.7m
109 mg of triethylamine and 133 mg of trichlorosilane were added to a solution consisting of g and 5 ml of xylene, stirred at 130° C. for 6 hours, and cooled to room temperature. Next, add 1.4 ml of 30% caustic soda aqueous solution and
After stirring at ℃ for 30 minutes, extraction with ether, washing the organic layer with water, drying with sodium sulfate, evaporation of the solvent, and treatment with an alumina column (solvent: benzene) yielded 35.8
mg of [Ib] was obtained.

[α]D 25=-303° (C=0.
49, chloroform) 1H NMR (CDCl3, 200MHz) δ 1
．． 35 (m, 6H), 3.49 (q, J=7.0Hz,
2H), 3.79 (m, 2H), 4.12 (m, 2H)
, 4.30 (s, 10H), 4.55 (m, 2H), 7
．． 1-7.3 (m, 20H) 31P NMR (CDC
l3,81MHz) δ 2.19

Reference Example 1 Production example of transpalladium complex At room temperature, dichlorobis(acetonitrile)palladium (
II) 14 mg and [Ib] 42 obtained in Example 4
．． After mixing 9 mg in chloroform, it was treated with a silica gel column (solvent: methylene chloride) to separate the orange component, which was recrystallized from a mixed solvent of methylene chloride and ether, with a yield of about 30%. A transpalladium complex was obtained. Melting point 230 ~ 235 ℃ (decomposition) Elemental analysis value (
As C48H44P2Cl2Fe2Pd) Actual value
C 59.10% H 4.54% Calculated value C 59.32% H 4.56%

1H NMR (CDCl3, 200M
Hz) δ 1.65 (td, |3JP-H +5JP
-H |=13.0 and |3JH-H |=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, 16
H), 7.9-8.0 (m, 4H), 13C NMR
(CDCl3, 50MHz) δ 19.88, 30
．． 90(t, |2JP-C +4JP-C |=18H
z), 67.61, 68.06, 70.14 (Cp),
72.74, 86.68, 91.71 (t, ｜2JP
-C +4JP-C |=10Hz), 127.08
(t, |3JP-C +5JP-C |=9Hz, m
eta), 127.23 (t, |3JP-C +5
JP-C |=7Hz, meta), 127.93 (
t, |1JP-C +3JP-C|=38Hz, ip
so), 129.12 (para), 130.59 (
para), 130.94(t, |1JP-C +3
JP-C |=43Hz, ipso), 133.46(
t, |2JP-C +4JP-C |=9Hz, ort
ho), 137.80(t, |2JP-C +4JP-
C |=11Hz, ortho), 31P NMR
(CDCl3, 81MHz) δ 25.11

0053
Reference Example 2 Production example of trans platinum complex At room temperature, 24.5 mg of trans dichlorobis(acetonitrile)platinum(II) and [Ib] obtained in Example 4
After mixing 55.6 mg in chloroform, 40
React for 12 hours at °C. A mixture of trans and cis forms (approximately 20:1) was obtained. A silica gel column treatment (solvent: dichloromethane) was carried out, and the orange component flowing out first was separated, and this was recrystallized from a mixed solvent of dichloromethane and ether to obtain a trans platinum complex with a yield of about 30%. A cis platinum complex was obtained from the orange component that flowed out later.

"Trans platinum complex" Melting point: 240-245°C (decomposition) Elemental analysis value (
As C48H44P2Cl2Fe2Pt) Actual value
C 54.06% H 4.04% Calculated value C 54.36% H 4.18%
1H NMR (CDCl3, 200MHz) δ 1
．． 66 (td, |3JP-H +5JP-H |=1
2.2 and |3JH-H |=6.6Hz,6H
), 3.76 (m, 2H), 4.06 (m, ｜2JP
-H +4JP-H |=4.0Hz, 2H), 4.3
1 (s, 10H), 4.39 (m, 2H), 4.64 (
m, 2H), 7.2-7.4 (m, 16H), 7.8-
7.9 (m, 4H), 13C NMR (CDCl3
, 50MHz) δ 19.98, 30.90(t, |
3J195Pt-C |=22Hz), 30.85(q
uint, |1JP-C +3JP-C |=27H
z), 67.10, 67.85, 69.71 (Cp),
72.55, 86.63, 91.62 (t, ｜3JP
-C +5JP-C |=8Hz), 126.97 (
t, |1JP-C +3JP-C |=46Hz,i
pso), 127.05 (t, |3JP-C +5
JP-C |=10Hz, meta), 127.24
(t, |3JP-C +5JP-C |=9Hz,i
meta), 129.19 (para), 129.90
(t, |1JP-C +3JP-C |=50Hz,i
pso), 130.60 (para), 133.48 (
t, |2JP-C +4JP-C |=9Hz, ort
ho), 137.53(t, |2JP-C +4JP-
C |=11Hz, ortho), 31P NMR (CDCl3, 81MHz) δ 2
1.41 (t, J195Pt-P = 2612Hz)

[
"Cis platinum complex" 1H NMR (CDCl3, 200MHz) δ 0
．． 7-016 (m, 6H), 3.74 (m, 2H), 3
．． 88 (s, 10H), 4.42 (m, 2H), 4.8
7 (m, 2H), 7.2-7.4 (m, 12H), 7.
5-7.6 (m, 4H), 7.9-8.0 (m, 4H)
J 31P NMR (CDCl3, 81MHz) δ 1
6.12 (t, J195Pt-P = 3668Hz)

[
Reference Example 3 Production Example of Palladium Complex 24.8 mg of [Ia] obtained in Example 3 and 8.71 mg of dichlorobis(acetonitrile)palladium(II) were added to about 4 ml of methylene chloride at room temperature.
Stirred for 30 minutes. Next, diethyl ether was added little by little to precipitate purple crystals. 28
mg of palladium complex was obtained.

[α]D 20=-712.3°(C=
0.334, methylene chloride)

Claims (7)

[Claims] Claim 1: An optical compound represented by the formula [I] (wherein, Ar represents an aryl group, X represents (CHR1)n, n represents a numerical value of 0 to 1, and R1 represents a lower alkyl group). Active biferrocene derivative. [Claim 2] An optical compound represented by the formula [II] (wherein, Ar represents an aryl group, X represents (CHR1)n, n represents a numerical value of 0 to 1, and R1 represents a lower alkyl group). A method for producing an optically active biferrocene derivative represented by formula [I] according to claim 1, which comprises reducing active biphosphinylferrocene. 3. An optically active biphosphinylferrocene represented by formula [II] according to claim 2. 4. The optically active biphosphinylferrocene according to claim 3, wherein n is 0. [Claim 5] Phosphinylferrocene represented by formula [III] (wherein Ar represents an aryl group) is reacted with a strong base and then reacted with a halogen to form a compound of formula [IV] (formula (wherein, Ar has the same meaning as above, and Y represents a halogen atom.) was obtained, and then homocoupled in the presence of a metal catalyst to obtain the formula [V] (formula 5. The optical method according to claim 4, wherein the dl-form of biphosphinylferrocene represented by Ar and Ar has the same meaning as above is obtained, and then this is optically resolved using an optically active organic acid. Method for producing active biphosphinylferrocene. 6. The optically active biphosphinylferrocene according to claim 3, wherein n is 1. [Claim 7] Optically active ferrocenylamine represented by formula [VI] (wherein, X represents CHR1, R1 represents a lower alkyl group, and R2 represents a lower alkyl group) in the presence of a strong base. It is reacted with halogens to obtain an optically active halogenoferrocenylamine represented by the formula [VII] (wherein, X, R1, and R2 have the same meanings as above, and Y represents a halogen atom), and then By treating with an alkyl halide and then reacting with diarylphosphine oxide, or by reacting diarylphosphine instead of diarylphosphine oxide and further oxidizing, the formula [VIII] (in the formula,
X, R1 and Y have the same meanings as above, and Ar represents an aryl group. 7. The method for producing optically active biphosphinyl ferrocene according to claim 6, which comprises obtaining an optically active halide ferrocenyl phosphine oxide represented by the following formula and then homocoupling it in the presence of a metal catalyst.