JP2000007691A - Production of optically active 2-(disubstituted phosphinyl)-2'-(substituted sulfonyloxy)-1,1'-binaphthyl - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optically active 2,2'-bis(disubstituted phosphinyl)-1,1'- binaphthyl which can be used, for example, as a raw material for a catalyst, for the asymmetric synthesis by reacting a specific 2,2'-dihydroxybinaphthyl sulfonate with a chloro disubstituted phosphine oxide in the presence of hydrogen, an amine, a Pd catalyst, and so on. SOLUTION: This compound shown by formula III is obtained inexpensively and simply by reacting an optically active 2,2'-dihydroxy-1,1'-binaphthyl sulfonate shown by formula I (R1 is an alkyl; a perfluoroalkyl, an aryl or a perfluoroaryl) with a chloro disubstituted phosphine oxide shown by formula II (R2 and R3 are each an aryl or a cycloalkyl) in the presence of hydrogen, an amine, a hydrogenating catalyst, and a palladium catalyst. This compound is useful, for example, as an intermediate to synthesize a monodentate optically active phosphine ligand for a catalyst for the asymmetric synthesis, for example, of optically active medicines, agrochemicals, perfumes, and liquid crystals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a monodentate optically active phosphine ligand MOP (Monode) of an asymmetric synthesis catalyst for producing optically active pharmaceuticals, agricultural chemicals, fragrances and liquid crystals.
The present invention relates to a method for producing optically active 2- (disubstituted phosphinyl) -2 ′-(substituted sulfonyloxy) -1,1′-binaphthyl, which is a synthetic intermediate of ntate Optically Active Phosphines.

[0002]

2. Description of the Related Art Optically active 2- (trifluoromethanesulfonyloxy) -2 '-(diphenylphosphinyl)-
A method for obtaining 1,1'-binaphthyl is described in Journal of Organic Chemistry (Journal).
of Organic Chemistry), 58 ,
1945 (1993) discloses a method of reacting optically active 2,2'-bis (trifluoromethanesulfonyloxy) -1,1'-binaphthyl with diphenylphosphine oxide in the presence of a palladium catalyst. Oxide was expensive and difficult to obtain industrially, so it could not be said to be a practical production method.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a simple optically active substance using a raw material which is inexpensive and industrially easily available.
An object of the present invention is to provide a process for producing-(disubstituted phosphinyl) -2 '-(substituted sulfonyloxy) -1,1'-binaphthyl.

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that in the presence of hydrogen, an amine, a hydrogenation catalyst and a palladium catalyst, the optically active 2,2 'is present.
-Optically active 2- (disubstituted phosphinyl)-is obtained by reacting sulfonic acid ester of dihydroxy-1,1'-binaphthyl with chlorodisubstituted phosphine oxide.
They have found that 2 '-(substituted sulfonyloxy) -1,1'-binaphthyl can be produced inexpensively and easily, and have completed the present invention.

That is, the present invention provides a compound represented by the following general formula (1):

[0006]

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[In the formula (1), R ¹ represents an alkyl group, a perfluoroalkyl group, an aryl group or a perfluoroaryl group. And a sulfonic acid ester of optically active 2,2'-dihydroxy-1,1'-binaphthyl represented by the following general formula (2):

[0008]

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[In the formula (2), R ² and R ³ may be the same or different and each represents an aryl group or a cycloalkyl group. A chlorodisubstituted phosphine oxide represented by the following general formula (3):

[0010]

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[In the formula (3), R ¹ , R ² and R ³ have the same meanings as above. Optically active 2- (disubstituted phosphinyl) -2 '-(substituted sulfonyloxy)-
Provided is a method for producing 1,1'-binaphthyl.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the optically active 2,2'-dihydroxy-1,1'-binaphthyl sulfonic acid ester represented by the general formula (1) which can be used in the present invention, R ¹ is preferably an alkyl group having 1 to 12 carbon atoms. (E.g., methyl, ethyl, butyl, hexyl, octyl, decyl, dodecyl, etc.), a perfluoroalkyl group having 1 to 20, preferably 1 to 10 carbon atoms (e.g., trifluoromethyl, nonafluorobutyl, perfluoro Hexyl, perfluorooctyl, perfluorodecyl, etc.), an aryl group (eg, phenyl, naphthyl, etc.), a perfluoroaryl group having 6 to 12 carbon atoms (eg, pentafluorophenyl, perfluoronaphthyl, perfluorotolyl, etc.) is there. Among the above, the alkyl group and the aryl group may further have a substituent, and examples of the substituent include fluoro, chloro, bromo, iodo, nitro, cyano, methyl, trifluoromethyl and the like.

Specifically, optically active 2,2'-bis (trifluoromethanesulfonyloxy) -1,1'-binaphthyl and optically active 2,2'-bis (nonafluorobutanesulfonyloxy) -1,1 ' -Binaphthyl, optically active 2,2'-bis (perfluorohexanesulfonyloxy) -1,1'-binaphthyl, optically active 2,2'-bis (perfluorooctanesulfonyloxy) -1,1 '
-Binaphthyl, optically active 2,2'-bis (methanesulfonyloxy) -1,1'-binaphthyl, optically active 2,
2'-bis (benzenesulfonyloxy) -1,1'-
Binaphthyl, optically active 2,2'-bis (p-toluenesulfonyloxy) -1,1'-binaphthyl and optically active 2,2'-bis (pentafluorobenzenesulfonyloxy) -1,1'-binaphthyl Can be

More preferably, optically active 2,2'-bis (trifluoromethanesulfonyloxy) -1,1'-
Binaphthyl, optically active 2,2'-bis (nonafluorobutanesulfonyloxy) -1,1'-binaphthyl, optically active 2,2'-bis (perfluorohexanesulfonyloxy) -1,1'-binaphthyl, optically active 2,2'-
Bis (perfluorooctanesulfonyloxy) -1,
1'-binaphthyl.

The optically active sulfonic acid ester of 2,2'-dihydroxy-1,1'-binaphthyl used in the present invention is a tetrahedron letter (Tetrahedro).
n Letters), 31 , 985 (1990). That is, it can be obtained by reacting optically active 2,2'-dihydroxy-1,1'-binaphthyl with various sulfonic anhydrides or various sulfonic halides in the presence of an amine base.

The amine which can be used in the present invention is preferably a tertiary amine, and may be any of monoamine, diamine, triamine and polyamine, and may be any of aliphatic, alicyclic and aromatic.

Specific examples of the amine include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-s-butylamine, tri-t-butylamine, diisopropylethylamine, dimethylcyclohexylamine, dicyclohexylethylamine, and tribenzyldiamine. Luamine, N-methylpiperidine, N, N-dimethylaniline, N, N-diethylaniline, 1,4-diazabicyclo [2.2.2] octane, tetramethylethylenediamine, 1,4-dimethylpiperazine, N-methylpyrrolidine , N-methylmorpholine, 1-methyl-2,
2,6,6-tetramethylpiperidine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, pyridine,
2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, 2,6-di-t
-Butylpyridine and the like.

Particularly preferred amines which can be used in the present invention include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-s-butylamine, tri-t-butylamine, diisopropylethylamine, dicyclohexylethylamine, N -Methylpiperidine, N-methylpyrrolidine, N-methylmorpholine, 1,4-dimethylpiperazine, 1-methyl-2,
2,6,6-tetramethylpiperidine, tetramethylethylenediamine, N, N-diethylaniline, 1,4-
Diazabicyclo [2.2.2] octane, pyridine,
2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, and 2,6-dimethylpyridine
Di-t-butylpyridine and the like. More preferably triethylamine, diisopropylethylamine,
1,4-diazabicyclo [2.2.2] octane, and N-methylpiperidine. Of these, two or more amines may be used in combination.

Optically active 2,2'-dihydroxy-1,
The amount of the amine to be used relative to the sulfonic acid ester of 1'-binaphthyl is preferably 4 to 8 moles, more preferably 5 to 7 moles.

The palladium catalyst that can be used in the present invention is preferably palladium / activated carbon, palladium black,
Palladium / barium sulfate, palladium / strontium carbonate, palladium / calcium carbonate, palladium / calcium carbonate-lead acetate, palladium / barium sulfate-
Quinoline, palladium / alumina, palladium sponge, palladium chloride, palladium acetate, palladium acetylacetonate, bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, dichloro [bis (triphenylphosphine)]
Palladium, dichloro [bis (diphenylphosphino)
Methane] palladium, dichloro [1,2-bis (diphenylphosphino) ethane] palladium, dichloro [1,
3-bis (diphenylphosphino) propane] palladium, dichloro [1,4-bis (diphenylphosphino)
Butane] palladium, dichloro (1,5-cyclooctadiene) palladium, dichlorobis (benzonitrile)
Examples include palladium catalysts such as palladium, dichlorobis (acetonitrile) palladium, and [bis (triphenylphosphine)] palladium acetate.

More preferably, tetrakis (triphenylphosphine) palladium, dichloro [bis (triphenylphosphine)] palladium, dichloro [bis (diphenylphosphino) methane] palladium, dichloro [1,2-bis (diphenylphosphino) palladium] Ethane] palladium, dichloro [1,3-bis (diphenylphosphino) propane] palladium, dichloro [1,4-bis (diphenylphosphino) butane] palladium, and dichloro (1,5-cyclooctadiene) palladium. .

The amount of the palladium catalyst used for the optically active sulfonic acid ester of 2,2'-dihydroxy-1,1'-binaphthyl is preferably 0.01% by weight to 5% by weight.
0% by weight, more preferably 5% to 20% by weight.

The hydrogenation catalyst that can be used in the present invention includes:
Preferably, platinum catalyst such as platinum oxide, platinum / activated carbon, platinum black, nickel catalyst such as reduced nickel, Raney nickel, Raney nickel with platinum, cobalt catalyst such as Raney cobalt, reduced copper, copper catalyst such as copper-chromium oxide, Zinc catalyst such as zinc-chromium oxide, ruthenium oxide, ruthenium catalyst such as ruthenium / activated carbon, rhodium / activated carbon, rhodium catalyst such as rhodium / alumina, rhodium-platinum oxide, rhenium catalyst such as rhenium oxide, palladium / activated carbon, palladium Black, palladium / barium sulfate, palladium / strontium carbonate, palladium / calcium carbonate, palladium / calcium carbonate-lead diacetate, palladium / barium sulfate-quinoline, palladium / alumina,
Palladium sponge, palladium chloride, palladium acetate, palladium acetylacetonate, bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, dichloro [bis (triphenylphosphine)] palladium, dichloro [bis (diphenylphosphino) methane Palladium, dichloro [1,2-bis (diphenylphosphino) ethane] palladium, dichloro [1,3-bis (diphenylphosphino) propane] palladium, dichloro [1,4-bis (diphenylphosphino) butane] palladium , Dichloro (1,5-cyclooctadiene), dichlorobis (benzonitrile) palladium, dichlorobis (acetonitrile) palladium, acetic acid [bis (triphenylphosphine)] palladium, etc. Umm catalyst, and the like.

The amount of the hydrogenation catalyst used for the optically active sulfonic acid ester of 2,2'-dihydroxy-1,1'-binaphthyl is preferably 0.01% by weight to 50% by weight, more preferably 0.1% by weight. It is 1% to 20% by weight.

The hydrogenation catalyst is particularly preferably a palladium catalyst. The amount of palladium on the support is preferably 0.5% to 30% by weight, more preferably 5% to 10% by weight. 2,2'-dihydroxy-1,
The amount of the palladium catalyst used for the optically active sulfonic acid ester of 1'-binaphthyl is preferably 1% by weight to 50% by weight, more preferably 10% by weight to 20% by weight.

A phosphine ligand can be used together with the palladium catalyst used in the present invention. The phosphine ligands that can be used are preferably triphenylphosphine, bis (diphenylphosphino) methane, 1,2-
Bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane and the like can be mentioned. More preferably, 1,2-bis (diphenylphosphino) ethane,
1,3-bis (diphenylphosphino) propane, 1,
4-bis (diphenylphosphino) butane. The amount of the phosphine ligand to be used with respect to the palladium catalyst is preferably 1 to 2 moles, more preferably 1.0 to 1.5 moles.

The chlorodisubstituted phosphine oxide used in the present invention is represented by the general formula (2). R ² and R ³ may be the same or different, but are preferably chlorodiarylphosphine oxide or chlorodicycloalkylphosphine oxide in which R ² and R ³ are the same.

In R ² and R ³ in the formula (2), the aryl group is preferably a phenyl group or a naphthyl group,
The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl,
Cyclododecyl).

These groups may further have one or more substituents. Preferred substituents are those having 1 to carbon atoms.
10 alkyl groups (eg, methyl, ethyl, n-butyl, s-butyl, t-butyl, hexyl, octyl, decyl, etc.), and cycloalkyl groups having 3 to 12 carbon atoms (eg, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexyl) Octyl, cyclododecyl and the like), an alkoxy group having 1 to 10 carbon atoms (for example, methoxy, ethoxy, n-butoxy, s-butoxy, t-butoxy, hexyloxy,
Octyloxy, decyloxy, etc.), a cycloalkyloxy group having 3 to 12 carbon atoms (eg, cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, cyclooctyloxy, cyclododecyloxy, etc.), a halogen atom (eg, a fluorine atom, a chlorine atom, Bromine atom,
And iodine atom), a perfluoroalkyl group having 1 to 10 carbon atoms (for example, trifluoromethyl, nanofluorobutyl, perfluorohexyl, perfluorooxyl,
Perfluorodecyl, etc.), amino group (eg, dimethylamino, diethylamino, dicyclohexylamino, pyrrolidino, piperidino, morpholino, N-methylpiperazino, diphenylamino, etc.), aryl group (eg, phenyl, naphthyl, pyridyl, etc.), perfluoroaryl (Eg, pentafluoromethyl, perfluoronaphthyl, perfluorotolyl, etc.), amide group (eg, acetamido, benzamide, etc.), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, cyclohexyloxycarbonyl, phenyloxycarbonyl, etc.), Examples thereof include an alkylthio group (eg, methylthio, ethylthio, cyclohexylthio, etc.) and an allylthio group (eg, phenylthio, naphthylthio, etc.).

Specifically, chlorodiphenylphosphine oxide, chlorodi (3-methylphenyl) phosphine oxide, chlorodi (4-methylphenyl) phosphine oxide, chlorobis (2,4-dimethylphenyl) phosphine oxide, chlorobis (3,5 -Dimethylphenyl) phosphine oxide, chlorobis (2,6-dimethylphenyl) phosphine oxide, chlorobis (2
4,6-trimethylphenyl) phosphine oxide, chlorobis (3,4,5-trimethylphenyl) phosphine oxide, chlorodi (4-t-butylphenyl) phosphine oxide, chlorobis (3,5-di-t-butylphenyl) phosphine Oxide, chlorodi (3-methoxyphenyl) phosphine oxide, chlorodi (4-methoxyphenyl) phosphine oxide, chlorobis (2,
4-dimethoxyphenyl) phosphine oxide, chlorobis (3,5-dimethoxyphenyl) phosphine oxide, chlorobis (2,6-dimethoxyphenyl) phosphine oxide, chlorobis (2,4,6-trimethoxyphenyl) phosphine oxide, chlorobis (3 , 4,
5-trimethoxyphenyl) phosphine oxide, chlorobis (3,5-dimethyl-4-methoxyphenyl) phosphine oxide,

Chlorodi (3-chlorophenyl) phosphine oxide, chlorodi (4-chlorophenyl) phosphine oxide, chlorobis (2,4-dichlorophenyl)
Phosphine oxide, chlorobis (3,5-dichlorophenyl) phosphine oxide, chlorobis (2,6-dichlorophenyl) phosphine oxide, chlorobis (2,4,6-trichlorophenyl) phosphine oxide, chlorobis (3,4,5-trichlorophenyl) Phosphine oxide, chlorodi (3-fluorophenyl)
Phosphine oxide, chlorodi (4-fluorophenyl) phosphine oxide, chlorobis (2,4-difluorophenyl) phosphine oxide, chlorobis (3
5-difluorophenyl) phosphine oxide, chlorobis (2,6-difluorophenyl) phosphine oxide, chlorobis (2,4,6-trifluorophenyl)
Phosphine oxide, chlorobis (3,4,5-trifluorophenyl) phosphine oxide, chlorobis (3
-Trifluoromethylphenyl) phosphine oxide,
Chlorobis (4-trifluoromethylphenyl) phosphine oxide, chlorobis (2,4-bistrifluoromethylphenyl) phosphine oxide, chlorobis (3,5-bistrifluoromethylphenyl) phosphine oxide, chlorobis (2,6-bistrifluoromethylphenyl) ) Phosphine oxide, chlorobis (2,
4,6-tristrifluoromethylphenyl) phosphine oxide, chlorobis (3,4,5-tristrifluoromethylphenyl) phosphine oxide,

Chlorobis (3-dimethylaminophenyl) phosphine oxide, chlorobis (4-dimethylaminophenyl) phosphine oxide, chlorobis (2
4-bisdimethylaminophenyl) phosphine oxide, chlorobis (3,5-bisdimethylaminophenyl) phosphine oxide, chlorobis (2,6-bisdimethylaminophenyl) phosphine oxide, chlorobis (2,4,6-trisdimethylaminophenyl) ) Phosphine oxide, chlorobis (3,4,5-trisdimethylaminophenyl) phosphine oxide, chlorobis (3-biphenyl) phosphine oxide, chlorobis (4-biphenyl) phosphine oxide, chlorobis (2,4-diphenylphenyl) phosphine oxide,
Chlorobis (3,5-diphenylphenyl) phosphine oxide, chlorobis (2,6-diphenylphenyl)
Phosphine oxide, chlorobis (2,4,6-triphenylphenyl) phosphine oxide, chlorobis (3,4,5-triphenylphenyl) phosphine oxide, chlorodi (α-naphthyl) phosphine oxide,
Chlorodi (β-naphthyl) phosphine oxide, chlorodi (6-methoxy-α-naphthyl) phosphine oxide, chlorodi (6-methoxy-β-naphthyl) phosphine oxide, chlorodi (3,4-methylenedioxyphenyl) phosphine oxide, chloro Examples include dicyclopropylphosphine oxide, chlorodicyclopentylphosphine oxide, chlorodicyclohexylphosphine oxide, chlorodicyclooctylphosphine oxide, chlorodicyclodecylphosphine oxide, chlorodicyclododecylphosphine oxide, and chlorocyclohexylphenylphosphine oxide.

The amount of the chlorodisubstituted phosphine oxide represented by the formula (2) of the present invention is preferably 1 to 1 mol based on the sulfonic acid ester of optically active 2,2'-dihydroxy-1,1'-binaphthyl. 3 times the mole,
More preferably, it is 1.5 to 2.5 times mol.

The solvent which can be used in the present invention is preferably N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2. -Imidazolidinone, dimethyl sulfoxide, acetonitrile and the like. More preferred are dimethyl sulfoxide and N, N-dimethylformamide.

The pressure of hydrogen used in the present invention is not particularly limited, but is preferably 100 kPa to 1 MPa. The method for introducing hydrogen is not limited, and the inside of the reaction vessel may be replaced with hydrogen or may be continuously introduced into the reaction vessel. Further, it may be introduced together with an inert gas such as nitrogen. Further, hydrogen adsorbed on a hydrogenation catalyst such as Raney nickel can also be used. At least twice the molar amount of the sulfonic acid ester of optically active 2,2'-dihydroxy-1,1'-binaphthyl is required. Usually, the reaction is carried out under a hydrogen atmosphere, so that a large excess is used. Formic acid, ammonium formate, sodium phosphite, hydrazine and the like can be used as a hydrogen source.

The reaction temperature of the present invention is preferably from 80 ° C to 160 ° C, more preferably from 100 ° C to 1 ° C.
40 ° C. The reaction is usually completed in 12 to 24 hours.

The reaction procedure in the present invention is optional, and includes a solvent, hydrogen, an amine, a hydrogenation catalyst, a palladium catalyst, an optically active sulfonate of 2,2'-dihydroxy-1,1'-binaphthyl, and chlorodisubstitution. The phosphine oxide may be added in any order.

The method of the present invention will be described in detail. An appropriate solvent is an amine, a hydrogenation catalyst, a palladium catalyst, an optically active sulfonic acid ester of 2,2'-dihydroxy-1,1'-binaphthyl, and chlorodichloromethane. A substituted phosphine oxide is added, the inside of the reaction system is replaced with hydrogen, and the mixture is heated and stirred.
The reaction mixture is filtered, and the filtrate is concentrated under reduced pressure. Water is added to the concentrated residue, the insolubles are collected by filtration, washed with water, and dried to obtain optically active 2- (disubstituted phosphinyl) -2 '-(substituted sulfonyloxy) -1,1'-binaphthyl. it can. Purification can be easily performed by column chromatography or recrystallization.

The 2- (disubstituted phosphinyl) -2 '-(substituted sulfonyloxy) -1,1'-binaphthyl represented by the formula (3) obtained by using the present invention is obtained by converting the substituted sulfonyloxy group to an alkoxy group. Alternatively, various monodentate optically active phosphine ligands useful for producing optically active pharmaceuticals, agricultural chemicals, fragrances, liquid crystals, etc. by converting to an alkyl group and converting a disubstituted phosphinyl group to a disubstituted phosphino group. (Journal of Organic Chemistry (Journal of Organic Chemistry)
Organic Chemistry), 58 , 19
45 (1993)).

[0040]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1 10% palladium / 0.5 g of activated carbon and 23 mg of palladium acetate were added to 10 ml of N, N-dimethylformamide.
(0.10 mmol), 43 mg (0.10 mmol) of 1,4-bis (diphenylphosphino) butane, 1.02 g of diisopropylethylamine (7.89 mmol)
l), (R) -2,2'-bis (trifluoromethanesulfonyloxy) -1,1'-binaphthyl 1.08 g
(1.96 mmol) and 1.08 g (4.56 mmol) of chlorodiphenylphosphine oxide were added, and the inside of the reaction vessel was depressurized and replaced with hydrogen gas. Mixture at 100 ° C
And stirred for 15 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Water was added to the concentrated residue, and the mixture was stirred, filtered, and the solid was washed with water and dried to obtain a crude product. This was purified by silica gel column chromatography (hexane / ethyl acetate = 1: 1) to give (R) -2- (trifluoromethanesulfonyloxy) -2 ′-(diphenylphosphinyl) -1,1′-binaphthyl 1 .12 g (1.8
6 mmol) in 95% yield.

[0042]

In the present invention, the reaction of a sulfonic acid ester of optically active 2,2'-dihydroxy-1,1'-binaphthyl with a chlorodisubstituted phosphine oxide in the presence of hydrogen, an amine and a palladium catalyst. To give optically active 2- (disubstituted phosphinyl) -2'-
(Substituted sulfonyloxy) -1,1′-binaphthyl is
It can be manufactured inexpensively and easily.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA02 AC81 BA05 BA19 BA20 BA21 BA25 BA37 BA44 BA45 BA47 BA48 BA61 BE20 4H039 CA90 CD20 CD90 4H050 AA02 BA05 BA07 BA16 BA17 BA30 BA32 BA37 BA55 BE20 WA15 WA26

Claims (4)

[Claims] 1. In the presence of hydrogen, an amine, a hydrogenation catalyst and a palladium catalyst, a compound represented by the following general formula (1): [In the formula (1), R ¹ represents an alkyl group, a perfluoroalkyl group, an aryl group, or a perfluoroaryl group. Optically active 2,2'-dihydroxy-
1,1'-binaphthyl sulfonic acid ester and the following general formula (2) [In formula (2), R ² and R ³ may be the same or different and each represents an aryl group or a cycloalkyl group. A chlorodisubstituted phosphine oxide represented by the following general formula (3): [In the formula (3), R ¹ , R ² and R ³ are as defined above. ] The method for producing optically active 2- (disubstituted phosphinyl) -2 '-(substituted sulfonyloxy) -1,1'-binaphthyl represented by the formula: 2. The optically active 2- (disubstituted phosphinyl) -2 ′-(substituted sulfonyloxy) -1,1 ′ according to claim 1, wherein the amine is a tertiary amine.
-Method for producing binaphthyl 3. A palladium catalyst comprising palladium / activated carbon, palladium black, palladium / barium sulfate, palladium / strontium carbonate, palladium / calcium carbonate, palladium / calcium carbonate-lead diacetate, palladium / barium sulfate-quinoline, palladium / alumina ,
Palladium sponge, palladium chloride, palladium acetate, palladium acetylacetonate, bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, dichloro [bis (triphenylphosphine)] palladium, dichloro [bis (diphenylphosphino) methane ] Palladium, dichloro [1,2-bis (diphenylphosphino) ethane] palladium, dichloro [1,3-bis (diphenylphosphino) propane] palladium, dichloro [1,4-bis (diphenylphosphino) butane] palladium , Dichloro (1,5-cyclooctadiene) palladium, dichlorobis (benzonitrile) palladium, dichlorobis (acetonitrile) palladium and acetic acid [bis (triphenylphosphine)] para 3. The optically active 2- (disubstituted phosphinyl) -2 '-(substituted sulfonyloxy) -1,1 according to claim 1 or 2, which is at least one member selected from the group consisting of Process for producing '-binaphthyl 4. The sulfonic acid ester of 2,2′-dihydroxy-1,1′-binaphthyl represented by the general formula (1) is converted to 2,2′-bis (trifluoromethanesulfonyloxy) -1,1′- Binaphthyl, 2,2'-bis (nonafluorobutanesulfonyloxy) -1,1'-binaphthyl, 2,2'-bis (perfluorohexanesulfonyloxy) -1,1'-binaphthyl, 2,2'-bis (Perfluorooctanesulfonyloxy) -1,1 '
-Binaphthyl, 2,2'-bis (methanesulfonyloxy) -1,1'-binaphthyl, 2,2'-bis (benzenesulfonyloxy) -1,1'-binaphthyl, 2,
2'-bis (p-toluenesulfonyloxy) -1,
4. The method according to claim 1, wherein the compound is at least one selected from the group consisting of 1'-binaphthyl and 2,2'-bis (pentafluorobenzenesulfonyloxy) -1,1'-binaphthyl. A process for producing the optically active 2- (disubstituted phosphinyl) -2 '-(substituted sulfonyloxy) -1,1'-binaphthyl according to any one of the preceding claims.