Background Art Conventionally, a large number of transition metal complexes are used as a catalyst for organic metal reaction. In particular, a transition metal complex, though it is expensive, has high activity and good stability and is easy to be handled, therefore a large number of synthetic reactions using it as a catalyst have been developed. In particular, asymmetric synthesis using chiral complex catalyst has shown remarkable progress, and a large number of reports on achieving a high efficiency of organic synthetic reaction, which was inefficient by conventional means, have been made.

Among them, especially an enormous number of developments in asymmetric reaction using a chiral complex having an optically active phosphine ligand as a catalyst have been made, and some of them have been used for industrialization. In addition, for example, among the complexes in which an optically active nitrogen compound is coordinated in the transition metal such as ruthenium, rhodium or iridium, many have an excellent performance as a catalyst for asymmetric synthesis. In order to enhance this performance as a catalyst, various optically active nitrogen compounds having a special structure have been developed so far (Chem. Rev. , 92,1051-1069 (1992), etc).

For example, a complex in which optically active N-p-toluenesulfonyl-1, 2-diphenylethylenediamine described in J. Am. Chem. Soc. , Vol.

117,7562-7563 (1995), J. Am. Chem. Soc. , Vol. 118, 4916-4917 (1996) is coordinated in ruthenium as a ligand has been reported. However, the reaction using this ligand is carried out in an organic solvent, and there have been no previous cases where it was carried out in water. In addition, a pharmaceutical intermediate or the like is tried to be produced by the method described therein, many of the intermediates are solid substances, therefore it is difficult to separate the obtained intermediate from the catalyst by a distillation procedure or the like.

As described above, separation between the product and the catalyst is a problem that cannot be avoided. Particularly in homogeneous catalytic reaction, since the catalyst to be used is easily dissolved in an organic phase, a complicated means such as distillation or recrystallization is necessary for separation between the product and the catalyst. It is conceivable that, as one of the solutions for this problem, if a water-soluble catalyst is used and reaction is carried out in a solvent system containing water, the product will be dissolved in an organic phase and the catalyst will be dissolved in an aqueous phase, whereby separation of the catalyst can be easily performed only by an extraction procedure. Under such a situation, a large number of reports on developing a water-soluble phosphine ligand have been made.

For example, in JP-A-5-170780, asymmetric hydrogenation using sulfonated-BINAP has been disclosed. However, there is no description on reuse of the catalyst dissolved in water after once performing hydrogenation.

In Tetrahedron Lett. , Vol. 42,4041-4043 (2001), transfer hydrogenation using a ligand sulfonated at the para-position of the phenyl group of benzenesulfonyl-1, 2-diaminocyclohexane has been reported. However, this reaction is performed in an isopropanol-water mixture solvent, therefore separation of the product have to be performed by distillation.

In Organic Letters, Vol. 5, No. 12,2103 (2003), a diphenyl-ethylenediamine derivative in which a tosyl group was introduced into one of the amino groups and which was sulfonated at the ortho-position of the phenyl group has been described, and it has been reported that asymmetric hydrogenation is performed in a water-dichloromethane mixture solvent using the diphenylethylenediamine derivative as an asymmetric hydrogenation catalyst. However, in Organic Letters, Vol. 5, No. 12,2103 (2003), there is no description on the synthesis method of the complex. In addition, when performing the asymmetric hydrogenation, it is necessary to use a phase transfer catalyst, which is expensive, and further there was a problem in the treatment of waste liquid and the like.

Disclosure of the Invention The present invention has been accomplished in view of the foregoing circumstances, and makes it an object to provide a recyclable water-soluble transition metal complex catalyst which is a novel metal complex catalyst capable of producing an optically active alcohol from a ketone with good yield and good optical purity by, for example, performing reaction using this as a catalyst, and which can be used in an aqueous solvent, and can be easily separated from the reaction product after reaction by a liquid separation means or the like.

The present invention relates to a water-soluble transition metal-diamine complex represented by the following formula (1) : (wherein Rl and R2 each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent or-SO2R13 (provided that R13 represents a hydrocarbon group which may have a substituent, a camphoryl group or a substituted amino group), R3 to R12 each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aralkyloxy group which may have a substituent, or-SO3R14 (provided that Rl4 represents a hydrogen atom or a metal atom), M represents a transition metal, X represents a halogen atom and L represents a ligand, provided that at least one of R3 to R12 is - SO3R14).

In addition, the present invention relates to an optically active compound of the foregoing water-soluble transition metal-diamine complex.

Further, the present invention relates to a method for producing the foregoing water-soluble transition metal-diamine complex, which comprises reacting a water-soluble diamine compound represented by the formula (2): (wherein Rl and R2 each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent or-So2Rl3 (provided that 13 represents a hydrocarbon group which may have a substituent, a camphoryl group or a substituted amino group), and R3 to R12 each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aralkyloxy group which may have a substituent, or-S03R14 (provided that R14 represents a hydrogen atom or a metal atom), provided that at least one of R3 to R12 is-SO3R14) with a transition metal compound represented by the formula (3): [MXmLnlp (3) (wherein M represents a transition metal, X represents a halogen atom, L represents a ligand, m represents 2 or 3, n represents 0 or 1 and p represents 1 or 2).

Still further, the present invention relates to a method for producing the foregoing water-soluble transition metal-diamine complex, in which the water-soluble diamine compound represented by the foregoing formula (2) is an optically active water-soluble diamine compound, and the obtained water-soluble transition metal-diamine complex is an optically active water-soluble transition metal-diamine complex.

Further, the present invention relates to a water-soluble diamine compound represented by the formula (2b): (wherein Rl and R2 each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent or-S02R13 (provided that R13 represents a hydrocarbon group which may have a substituent, a camphoryl group or a substituted amino group), and R3, Rs to R8 and Rl° to R12 each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aralkyloxy group which may have a substituent, or-SO3R14 (provided that R14 represents a hydrogen atom or a metal atom).

Further, the present invention relates to an optically active compound of the foregoing water-soluble diamine compound.

Still further, the present invention relates to a chiral catalyst comprising the foregoing optically active water-soluble transition metal-diamine complex.

Further, the present invention relates to a chiral catalyst comprising the foregoing optically active water-soluble diamine compound and a transition metal compound represented by the formula (3): [MXmLn] p (3) (wherein M represents a transition metal, X represents a halogen atom, L represents a ligand, m represents 2 or 3, n represents 0 or 1 and p represents 1 or 2).

Further, the present invention relates to a method for producing an optically active secondary alcohol, which comprises subjecting a ketone to asymmetric hydrogenation in an aqueous solvent in the presence of the chiral catalyst comprising the optically active water-soluble transition metal-diamine complex represented by the following formula (la) : (wherein * represents an asymmetric carbon atom, Rl and R2 each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent or - SO2R13 (provided that R13 represents a hydrocarbon group which may have a substituent, a camphoryl group or a substituted amino group), R3 to R12 each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aralkyloxy group which may have a substituent, or-S03R14 (provided that R14 represents a hydrogen atom or a metal atom), M represents a transition metal, X represents a halogen atom and L represents a ligand, provided that at least one of R3 to R12 is-SO3R14) of claim 3 and/or the chiral catalyst comprising the optically active water-soluble diamine compound represented by the formula (2c): (wherein * represents an asymmetric carbon atom, Ri and Ra each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent or - SO2R13 (provided that R13 represents a hydrocarbon group which may have a substituent, a camphoryl group or a substituted amino group), and R3, R5 to R8 and Rl° to R12 each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aralkyloxy group which may have a substituent, or-S03R14 (provided that R14 represents a hydrogen atom or a metal atom) of claim 7 and a transition metal compound represented by the formula (3): [MX,,, Lnlp (3) (wherein M represents a transition metal, X represents a halogen atom, L represents a ligand, m represents 2 or 3, n represents 0 or 1 and p represents 1 or 2).

The present invention relates to a method for producing an optically active secondary alcohol represented by the formula (5): (wherein * represents an asymmetric carbon, and R21 and R22 each independently represent a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent or a ferrocenyl group (provided that R21 and R22 are not identical), or R21 and R22 may be bound to each other to form a ring together with the carbon atom of the carbonyl group), which comprises subjecting a ketone represented by the formula (4): (wherein R21 and R22 are the same as above) to asymmetric hydrogenation in an aqueous solvent in the presence of any of the foregoing chiral catalysts.

Further, the present invention relates to the forgoing method for producing the optically active secondary alcohol, wherein the asymmetric hydrogenation is transfer hydrogenation.

Still further, the present invention relates to the foregoing method for producing the optically active secondary alcohol, in which the chiral catalyst is recycled after use.

In the asymmetric hydrogenation using the optically active water-soluble transition metal-diamine complex of the present invention as a catalyst, the catalyst can be recycled, which leads to reduction of cost. In addition, the asymmetric hydrogenation using the optically active water-soluble transition metal-diamine complex of the present invention as a catalyst can be carried out in an aqueous solvent, therefore, it can be said that it is an asymmetric hydrogenation considering the environmental aspect.

Best Mode for Carrying Out the Invention In the foregoing formulae (1), (2) and (2b), examples of the hydrocarbon group which may have a substituent represented by R1 and R2 include a hydrocarbon group and a substituted hydrocarbon group.

Examples of the hydrocarbon group include, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group and the like.

The alkyl group may be linear, branched or cyclic, and examples include, for example, an alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.

Specific examples include, for example, methyl, ethyl, n-propyl, 2-propyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, tert-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, heptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

The alkenyl group may be linear or branched, and examples include, for example, an alkenyl group having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms. Specific examples include, for example, ethenyl, propenyl, 1-butenyl, pentenyl, hexenyl and the like.

The alkynyl group may be linear or branched, and examples include, for example, an alkynyl group having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms. Specific examples include, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl, pentynyl, hexynyl and the like.

Examples of the aryl group include, for example, an aryl group having 6 to 14 carbon atoms, and specific examples include phenyl, tolyl, xylyl, 1-naphthyl, 2-naphthyl, anthryl and the like.

Examples of the aralkyl group include a group in which at least one hydrogen atom of the foregoing alkyl group was substituted by the foregoing aryl group, and for example, an aralkyl group having 7 to 15 carbon atoms is preferred. Specific examples include, for example, benzyl, 2-phenethyl, 1-phenylpropyl, 3-naphthylpropyl and the like.

Preferred examples of the hydrocarbon group for Rl and R2 include an alkyl group, aryl group and aralkyl group.

Examples of the substituted hydrocarbon group (a hydrocarbon group having a substituent) include a hydrocarbon group in which at least one hydrogen atom of the foregoing hydrocarbon group was substituted by a substituent, and specific examples include, for example, a substituted alkyl group, a substituted aryl group, a substituted alkenyl group, a substituted alkynyl group, a substituted aralkyl group and the like.

Examples of the substituent include a hydrocarbon group, a halogen atom, a halogenated hydrocarbon group, an alkoxy group, an aryloxy group, an aralkyloxy group, a substituted amino group and the like.

The hydrocarbon group as the substituent is the same as the foregoing hydrocarbon group.

Examples of the halogen atom as the substituent include fluorine, chlorine, bromine, iodine and the like.

Examples of the halogenated hydrocarbon group as the substituent include a group in which at least one hydrogen atom of the foregoing hydrocarbon group was substituted by a halogen (e. g. , fluorine-substituted, chlorine-substituted, bromine-substituted, iodine-substituted and the like). Preferred examples of the halogenated hydrocarbon group include, for example, a halogenated alkyl group and the like. Preferred examples of the halogenated alkyl group include, for example, a halogenated alkyl group having 1 to 10 carbon atoms. Specific examples thereof include, for example, chloromethyl, bromomethyl, 2-chloroethyl, 3-bromopropyl, fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, fluoropentyl, fluorohexyl, fluoroheptyl, fluorooctyl, fluorononyl, fluorodecyl, difluoromethyl, difluoroethyl, fluorocyclohexyl, trifluoromethyl, 2,2, 2-trifluoroethyl, 3,3, 3-trifluoropropyl, pentafluoroethyl, 3,3, 4,4, 4-pentafluorobutyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, perfluoroisobutyl, perfluoro-tert-butyl, perfluoro-sec-butyl, perfluoropentyl, perfluoroisopentyl, perfluoro-tert-pentyl, perfluoro-n-hexyl, perfluoroisohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, 2-perfluorooctylethyl, perfluorocyclopropyl, perfluorocyclopentyl, perfluorocyclohexyl and the like.

The alkoxy group as the substituent may be linear, branched or cyclic, and examples include, for example, an alkoxy group having 1 to 6 carbon atoms. Specific examples thereof include, for example, methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropyloxy, n-hexyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 5-methylpentyloxy, cyclohexyloxy and the like.

Examples of the aryloxy group as the substituent include, for example, an aryloxy group having 6 to 14 carbon atoms, and specific examples thereof include, for example, phenoxy, naphthyloxy, anthryloxy and the like.

Examples of the aralkyloxy group as the substituent include, for example, an aralkyloxy group having 7 to 12 carbon atoms, and specific examples thereof include, for example, benzyloxy, 2-phenethyloxy, 1-phenylpropoxy, 2-phenylpropoxy, 3-phenylpropoxy, 1-phenylbutoxy, 2-phenylbutoxy, 3-phenylbutoxy, 4-phenylbutoxy, 1-phenylpentyloxy, 2-phenylpentyloxy, 3-phenylpentyloxy, 4-phenylpentyloxy, 5-phenylpentyloxy, 1-phenylhexyloxy, 2-phenylhexyloxy, 3-phenylhexyloxy, 4-phenylhexyloxy, 5-phenylhexyloxy, 6-phenylhexyloxy, and the like.

Examples of the substituted amino group as the substituent include an amino group in which 1 or 2 hydrogen atoms of the amino group was substituted by a substituent such as an amino protective group. As the amino protective group as the substituent of the substituted amino group, any can be used as long as it is generally used as an amino protective group, and examples include the one described in, for example, "PROTECTIVE GROUPS IN ORGANIC SYNTHESIS THIRD EDITION (JOHN WILEY & SONS, INC. (1999) "as an amino protective group and the like. Specific examples of the amino protective group include, for example, an alkyl group, an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, a substituted sulfonyl group and the like.

The alkyl group, aryl group and aralkyl group for the foregoing amino protective group are the same as the respective groups described in the foregoing hydrocarbon group.

The acyl group may be linear, branched or cyclic, and examples include, for example, an acyl group having 1 to 20 carbon atoms derived from a carboxylic acid such as an aliphatic carboxylic acid, an aromatic carboxylic acid or the like. Specific examples include, for example, formyl, acetyl, propionyl, butyryl, pivaloyl, pentanoyl, hexanoyl, lauroyl, stearyl, benzoyl and the like.

The alkoxycarbonyl group may be linear, branched or cyclic, and examples include, for example, an alkoxycarbonyl group having 2 to 20 carbon atoms. Specific examples thereof include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 2-propoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, lauryloxycarbonyl, stearyloxycarbonyl, cyclohexyloxycarbonyl and the like.

Examples of the aryloxycarbonyl group include, for example, an aryloxycarbonyl group having 7 to 20 carbon atoms and the specific examples thereof include phenoxycarbonyl, naphthyloxycarbonyl and the like.

Examples of the aralkyloxycarbonyl group include, for example, an aralkyloxycarbonyl group having 8 to 20 carbon atoms, and the specific examples thereof include benzyloxycarbonyl, phenethyloxycarbonyl, 9-fluorenylmethyloxycarbonyl and the like.

Examples of the substituted sulfonyl group include, for example, a substituted sulfonyl group represented by Ra-SO2- (Ra represents a hydrocarbon group, a substituted hydrocarbon group or a substituted amino group). The hydrocarbon group, substituted hydrocarbon group and substituted amino group represented by Ra are the same as the respective groups described above. Specific examples of the substituted sulfonyl group include, for example, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl,-S02N (CH3) 2 and the like.

Specific examples of the amino group substituted with an alkyl group, namely alkyl-substituted amino group include, for example, mono-and di-alkylamino groups such as N-methylamino, N, N-dimethylamino, N, N-diethylamino, N, N-diisopropylamino, N-cyclohexylamino and the like. Specific examples of the amino group substituted with an aryl group, namely aryl-substituted amino group include, for example, mono-and di-arylamino groups such as N-phenylamino, N, N-diphenylamino, N-naphthylamino, N-naphthyl-N-phenylamino and the like. Specific examples of the amino group substituted with an aralkyl group, namely aralkyl-substituted amino group include, for example, mono-and d-aralkyl amino groups such as N-benzylamino, N, N-dibenzylamino and the like. Specific examples of the amino group substituted with an acyl group, namely acylamino group include, for example, formylamino, acetylamino, propionylamino, pivaloylamino, pentanoylamino, hexanoylamino, benzoylamino and the like.

Specific examples of the amino group substituted with an alkoxycarbonyl group, namely alkoxycarbonyl-amino group include, for example, methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, n-butoxycarbonylamino, tert-butoxycarbonylamino, pentyloxycarbonylamino, hexyloxycarbonylamino and the like.

Examples of the amino group substituted with an aryloxycarbonyl group; namely aryloxycarbonylamino group include, for example, an amino group in which one hydrogen atom of the amino group was substituted by the foregoing aryloxycarbonyl group, and specific examples thereof include phenoxycarbonylamino, naphthyloxycarbonylamino and the like.

Specific examples of the amino group substituted with an aralkyloxycarbonyl group, namely aralkyloxycarbonylamino group include, for example, benzyloxycarbonylamino and the like.

Specific examples of the amino group substituted with a substituted sulfonyl group include-NHS02CH3,-NHS02C6H5,-NHSO2C6H4CH3,-NHS02CF3, - NHS02N (CH3) 2 and the like.

In the foregoing formulae (1), (2) and (2b), the hydrocarbon group which may have a substituent and the substituted amino group represented by R13 in-SO2R13 represented by R'and W may be the same as the one described above. In the case where the hydrocarbon group which may have a substituent is a substituted hydrocarbon group, preferred examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl-substituted amino group having 1 to 5 carbon atoms, an acylamino group having 2 to 3 carbon atoms, and the like.

In the foregoing formulae (1), (2) and (2b), the hydrocarbon group which may have a substituent represented by R3 to R12 may be the same as the hydrocarbon group which may have a substituent described in the foregoing Rl and R2.

Examples of the heterocyclic group which may have a substituent include a heterocyclic group and a substituted heterocyclic group. Examples of the heterocyclic group include an aliphatic heterocyclic group and an aromatic heterocyclic group.

Examples of the aliphatic heterocyclic group include, for example, a 5-to 8-membered, preferably 5-or 6-membered monocyclic aliphatic heterocyclic group, polycyclic aliphatic heterocyclic group and condensed ring aliphatic heterocyclic group having 2 to 14 carbon atoms and at least one, preferably 1 to 3 heteroatoms such as a nitrogen atom, an oxygen atom and/or a sulphur atom, etc. Specific examples of the aliphatic heterocyclic group include, for example, pyrrolidyl-2-one, piperidino, piperazinyl, morpholino, morpholinyl, tetrahydrofuryl, tetrahydropyranyl and the like.

Examples of the aromatic heterocyclic include, for example, a 5-to 8-membered, preferably 5-or 6-membered monocyclic heteroaryl group, polycyclic heteroaryl group and condensed ring heteroaryl group having 2 to 15 carbon atoms and at least one, preferably 1 to 3 heteroatoms such as a nitrogen atom, an oxygen atom and/or a sulphur atom, etc. Specific examples thereof include furyl, thienyl, pyridyl, pyrimidyl, pyrazyl, pyridazyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, benzofuryl, benzothienyl, quinolyl, isoquinolyl, quinoxalyl, phthalazinyl, quinazolyl, naphthyridyl, cinnolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, acridyl, acridinyl and the like.

Examples of the substituted heterocyclic group (heterocyclic group having a substituent) include a heterocyclic group in which at least one hydrogen atom of the foregoing heterocyclic group was substituted by a substituent. Examples of the substituted heterocyclic group (heterocyclic group having a substituent) include a substituted aliphatic heterocyclic group and a substituted aromatic heterocyclic group.

The substituent may be the same as the substituent for the hydrocarbon group which may have a substituent described in the foregoing Rl and R2.

The alkoxy group which may have a substituent, the aryloxy group which may have a substituent and the aralkyloxy group which may have a substituent may be the same as the alkoxy group which may have a substituent, the aryloxy group which may have a substituent and the aralkyloxy group which may have a substituent, which are the substituents for the hydrocarbon group which may have a substituent described in the foregoing Rl and R2.

In the foregoing formulae (1), (2) and (2b), examples of the metal atom represented by R14 in-S03R14 represented by R3 to R12 and R14 in-S03R14 in the formula (2b) include an alkali metal, an alkaline earth metal and the like.

Examples of the alkali metal include, for example, lithium, sodium, potassium, rubidium, caesium and the like.

Examples of the alkaline earth metal include, for example, magnesium, calcium, strontium, barium and the like.

Examples of the transition metal represented by M in the foregoing formula (1) include, for example, transition metals in groups VIII to IX of the periodic table, and preferred are, for example, ruthenium, rhodium, iridium and the like.

Examples of the halogen atom represented by X in the formula (1) include fluorine, chlorine, bromine, iodine and the like, and preferred are chlorine, bromine, iodine and the like.

As the ligand represented by L in the formula (1), a neutral ligand is preferred.

Examples of the neutral ligand include an aromatic compound which may be substituted with an alkyl group, an olefin compound, other neutral ligands and the like.

Examples of the aromatic compound which may be substituted with an alkyl group include an unsubstituted aromatic compound and alkyl-substituted aromatic compound. Examples of the unsubstituted aromatic compound include benzene and the like. Examples of the alkyl-substituted aromatic compound include, for example, an aromatic compound in which at least one hydrogen atom of the foregoing aromatic compound was substituted by an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, isopropyl and the like. Specific examples of the alkyl-substituted aromatic compound include, for example, toluene, p-cymene, hexamethylbenzene, 1,3, 5-trimethylbenzene (mesitylene) and the like.

Examples of the olefin compound include, for example, ethylene, cyclopentadiene, 1, 5-cyclooctadiene (cod), norbornadiene (nbd), pentamethylcyclopentadiene and the like.

Examples of other neutral ligands include N, N-dimethylformamide (DMF), acetonitrile, benzonitrile, acetone, chloroform and the like.

In the water-soluble transition metal-diamine complexes represented by the formula (1), both of a racemic compound and an optically active compound are included, however, an optically active water-soluble transition metal-diamine complex represented by the following formula (la) : (wherein * represents an asymmetric carbon atom, and Rl to Rl2, M, X and L are the same as above) is more preferred.

Preferred examples of the water-soluble transition metal-diamine complex represented by the formula (1) include, for example, a water-soluble transition metal-diamine complex represented by the following formula (lb) : (wherein R1 to R3, R5 to R8, Rl° to R12, R, M, X and L are the same as above).

Preferred examples of the water-soluble transition metal-diamine complex represented by the formula (la) include, for example, an optically active water-soluble transition metal-diamine complex represented by the following formula (1c) : (wherein Rl to R3, Rs to R8, Rl° to R, R, M, X, L and * are the same as above).

The optically active water-soluble transition metal-diamine complex represented by the formula (1c) is also a preferred example of the water-soluble transition metal-diamine complex represented by the formula (1b).

Examples of the optically active water-soluble transition metal-diamine complex of the present invention include (1R, 2R), (1S, 2S), (1R, 2S) and (1S, 2R) forms, and preferred examples include (1R, 2R) and (1S, 2S) forms.

Specific examples of the optically active water-soluble transition metal-diamine complex represented by the formula (1c) include, for example, the following compounds and the like: In the water-soluble diamine compound represented by the formula (2), both of a racemic compound and an optically active compound are included, however, an optically active water-soluble diamine compound represented by the following formula (2a): (wherein Rl to R12 and * are the same as above) is more preferred.

Preferred examples of the water-soluble diamine compound represented by the formula (2) include, for example, a water-soluble diamine compound represented by the following formula (2b): (wherein Ri to R3, Rs to R8, Rl° to R12, and R14 are the same as above).

Preferred examples of the water-soluble diamine compound represented by the formula (2b) include, for example, an optically active water-soluble diamine compound represented by the following formula (2c): (wherein R1 to R3, R5 to R8, R10 to R12, R14, and * are the same as above), and more preferred examples include an optically active water-soluble diamine compound represented by the following formula (2e): (wherein R2, R3, R 5 to R8, Rl° to R14, and * are the same as above).

Examples of the optically active water-soluble diamine compound represented by the formula (2c) of the present invention include (1R, 2R), (1S, 2S), (1R, 2S) and (IS, 2R) forms, and preferred examples include (1R, 2R) and (1S, 2S) forms.

Specific examples of the optically active water-soluble diamine compound represented by the foregoing formula (2c) include, for example, (1R, 2R)-1, 2-di (4-sodium oxysulfonylphenyl) ethylenediamine, (IS, 2S)-1, 2-di (4-sodium oxysulfonylphenyl) ethylenediamine and the like.

Specific examples of the optically active water-soluble diamine compound represented by the foregoing formula (2e) include, for example, (1R, 2R)-(N-benzensulfonyl)-1, 2-di (4-sodium oxysulfonylphenyl)-ethylenediamine, (IS, 2S)-(N-benzensulfonyl)-1, 2-di (4-sodium oxysulfonylphenyl) ethylenediamine and the like.

Specific examples of the transition metal compound represented by the formula (3) which is used in the present invention include, for example, [RuCl2 (benzene) 2, [RuBr2 (benzene) 2, [RuI2 (benzene) 2, [RuCl2 (p-cymene)] 2, [RuBr2 (p-cymene)] 2, [RuI2 (p-cymene)] 2, [RuCl2 (hexamethylbenzene)] 2, [RuBr2 (hexamethylbenzene)] 2, [RuI2 (hexamethylbenzene)] 2, [RuCl2 (mesitylene)] 2, [RuBr2 (mesitylene)] 2, [RuI2 (mesitylene)] 2, [RuCl2 (pentamethylcyclopentadiene)] 2, [RuBr2 (pentamethylcyclopentadiene)] 2, [RuI2 (pentamethylcyclopentadiene)] 2, [RuCl2 (cod)] n) [RuBr2 (code)]n, [RuI2(cod)]n, [RuCl2(nbd)]n, [RuBr2 (nbd)]n, [RuI2(nbd)]n (wherein n represents a positive number), RuCl3 hydrate, RuBr3 hydrate, RuI3 hydrate, [RhCl2 (pentamethylcyclopentadiene)] 2, [RhBr2 (pentamethylcyclopentadiene)] 2, [RhI2 (pentamethylcyclopentadiene)] 2, [RhCl2 (cod)] 2, [RhBr2 (cod)] 2, [RhI2 (cod)] 2, [RhCl2 (nbd)] 2, [RhBr2 (nbd)] 2, [RhI2 (nbd)] 2, RhCl3 hydrate, RhBr3 hydrate, RhI3 hydrate, [IrCl2 (pentamethylcyclopentadiene)] 2, [IrBr2 (pentamethylcyclopentadiene)] 2, [IrI2 (pentamethylcyclopentadiene)] 2, [IrCl2 (cod)] 2, [IrBr2 (cod)] ]2, [IrI2 (cod)] 2, [IrCl2 (nbd)] 2, [IrBr2 (nbd)] 2, [IrI2 (nbd)] 2, IrCl3 hydrate, IrBr3 hydrate, Iris hydrate and the like.

The water-soluble transition metal-diamine complex represented by the foregoing formula (1) of the present invention can be produced, for example, as follows.

1) Introduction of a substituted sulfonyl group at the N-position.

Introduction of a substituted sulfonyl group at the N-position can be carried out by a known method.

First, a compound into which a substituted sulfonyl group is to be introduced at the N-position, for example a diamine such as diphenylethylenediamine, preferably optically active diphenylethylenediamine is reacted with a sulfonylating agent in an appropriate solvent, if necessary, in the presence of a base, whereby N-mono or di (substituted sulfonyl)-diphenylethylene-diamine, preferably optically active N-mono- (substituted sulfonyl) -diphenylethylenediamine [a water-soluble diamine compound in which either Rl or R2 is-So2R13 (Rl3 is the same as above) in the foregoing formula (2a) ] or optically active N-di (substituted sulfonyl) -diphenylethylenediamine [a water-soluble diamine compound in which Rl and R2 are-SO2R13 (Ri3 is the same as above) in the foregoing formula (2a) ] can be obtained. In addition, the foregoing diphenylthylenediamine may have a substituent in the phenyl group.

Examples of the sulfonylating agent include, for example, a sulfonylhalide represented by the formula (6): Rl3-So2-Xl (6) (wherein Xl represents a halogen atom and R13 is the same as above).

In the formula (6), examples of the halogen atom represented by Xl include fluorine, chlorine bromine, iodine and the like.

Specific examples of the sulfonylhalide represented by the formula (6) include, for example, methanesulfonyl chloride, ethanesulfonyl chloride, benzenesulfonyl chloride, p-toluenesulfonyl chloride, trifluoromethanesulfonyl chloride, 2,4, 6-mesithylsulfonyl chloride, 2,4, 6-triisopropylbenzenesulfonyl chloride, 4-methoxybenzenesulfonyl chloride, 4-chlorobenzenesulfonyl chloride and the like.

The amount of the sulfonylating agent to be used is selected from the range of generally from 0.8 to 5 moles, preferably from 1 to 2 moles, more preferably from 1 to 1.2 moles relative to 1 mole of diphenylethylenediamine as needed.

Examples of the base include an inorganic base, an organic base and the like.

Examples of the inorganic base include, for example, salts and hydroxides of an alkali metal or an alkaline earth metal such as potassium carbonate, potassium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, sodium hydroxide, magnesium carbonate and calcium carbonate, metal hydrides such as sodium hydride, sodium borohydride and aluminum lithium hydride and the like.

Examples of the organic base include, for example, salts of an alkali metal or an alkaline earth metal such as potassium methoxide, sodium methoxide, lithium methoxide, sodium ethoxide, potassium isopropoxide, potassium tert-butoxide, potassium naphthalenide, sodium acetate, potassium acetate, magnesium acetate and calcium acetate, organic amines such as triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine, 1, 5-diazabicyclo [4.3. 0] non-5-ene, 1, 8-diazabicyclo [5.4. 0] undec-7-ene, tri-n-butylamine and N-methylmorpholine, organic metal compounds such as magnesium methyl bromide, magnesium ethyl bromide, magnesium propyl bromide, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium and tert-butyl lithium, quaternary ammonium salt and the like.

Among these bases, the organic amines are particularly preferred.

The amount of the base to be used is selected from the range of generally from 1.0 to 2.0 equivalent amounts, preferably from 1. 1 to 1.2 equivalent amounts relative to the diamine as needed.

Examples of the solvent to be used for reaction include, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride and o-dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether, dimethoxyethane, ethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane and 1, 3-dioxolane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as methyl acetate, ethyl acetate, n-butyl acetate and methyl propionate, amides such as formamide, N, N-dimethylformamide and N, N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, cyano containing organic compounds such as acetonitrile, N-methylpyrrolidone, water and the like. These solvents may be used alone or in combination of two or more as needed.

The amount of the solvent to be used is selected from the range of generally from 2 to 10 times, preferably from 5 to 10 times the volume of the diamine as needed.

The reaction temperature is selected from the range of generally from 0 to 50°C, preferably from 0 to 10°C as needed.

The reaction time is selected from the range of generally from 3 to 20 hours, preferably from 5 to 10 hours as needed.

The obtained N-mono or di (substituted sulfonyl)-diphenylethylenediamine, preferably optically active N-mono or di (substituted sulfonyl)-diphenylethylene-diamine may be subjected to an aftertreatment, purification or the like as needed after the reaction.

Specific methods for the aftertreatment include known separation and purification methods such as solvent extraction, changing liquid property, solvent replacement, salting out, crystallization, recrystallization, and various chromatographies.

2) Sulfonation Sulfonation of the N-mono or di (substituted sulfonyl)-diphenylethylenediamine, preferably the optically active N-mono or di (substituted sulfonyl) -diphenylethylenediamine obtained in the foregoing 1), or diphenylethylenediamine, preferably optically active diphenylethylenediamine can be easily carried out by a known method, for example, using concentrated sulfuric acid or fuming sulfuric acid.

In the present invention, it is preferred that first, a substituted sulfonyl group be introduced, then sulfonation be performed.

More specifically, by performing sulfonation of the N-mono or di (substituted sulfonyl)-diphenylethylene-diamine, preferably the optically active N-mono or di (substituted sulfonyl)-diphenylethylenediamine obtained in the foregoing 1), or diphenylethylenediamine, preferably optically active diphenylethylenediamine in a mixed solution of fuming sulfuric acid (30% SO3-H2S04) and concentrated sulfuric acid, from the diphenylethylenediamine into which a substituted sulfonyl group was introduced, a water-soluble diamine compound represented by the formula (2d): (wherein R2, R3, R5 to R8 and R10 to R14 are the same as above), preferably an optically active water-soluble diamine compound represented by the foregoing formula (2e) can be obtained, or a water-soluble diamine compound represented by the formula (2f), in which Rl and R2 are a hydrogen atom in the foregoing formula (2) : (wherein R3, Rs to R8, R10 to R12 and R14 are the same as above), preferably an optically active water-soluble diamine compound represented by the formula (2g), in which Rl and R2 are a hydrogen atom in the foregoing formula (2a) : (wherein R3, Rs to R8, Rl° to Rl2, Rl4 and * are the same as above) can be obtained.

Also, from the diphenylethylenediamine into which a substituted sulfonyl group was not introduced, a water-soluble diamine compound represented by the foregoing formula (2f), preferably a compound represented by the foregoing formula (2g) can be obtained.

After finishing the reaction, if necessary, neutralization is optionally carried out with an aqueous alkali solution. Examples of the aqueous alkali solution used for neutralization include an aqueous solution of sodium hydroxide, aqueous solution of potassium hydroxide and the like.

The obtained water-soluble diamine compound, preferably optically active water-soluble diamine compound may be subjected to an aftertreatment, purification or the like as needed after the reaction. Specific methods and the like for the aftertreatment are as described above.

3) Sulfamidation (in the case of a water-soluble diamine compound in which a substituted sulfonyl group was not introduced at the N-position) Sulfamidation can be carried out by a known method such as the method described in the foregoing 1). For example, by reacting the water-soluble diamine compound represented by the foregoing formula (2f), preferably the optically active water-soluble diamine compound represented by the foregoing formula (2g) obtained in the foregoing 2) with the foregoing sulfonylating agent in an appropriate solvent, and if necessary in the presence of the base as described above, a water-soluble diamine compound represented by the foregoing formula (2d), preferably an optically active water-soluble diamine compound represented by the foregoing formula (2e) can be obtained.

The amount of the sulfonylating agent to be used is selected from the range of generally from 0.8 to 5 moles, preferably from 1 to 2 moles, more preferably from 1 to 1.2 moles relative to 1 mole of the water-soluble diamine compound as needed.

The amount of the base to be used is selected from the range of generally from 2 to 5 equivalent amounts, preferably from 2 to 2.5 equivalent amounts relative to the water-soluble diamine compound as needed.

Examples of the solvent include the solvents described in the foregoing (1), and preferred examples include, for example, amides such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide and the like. These solvents may be used alone or in combination of 2 or more as needed. Among these solvents, N, N-dimethylformamide is preferred since it dissolves the water-soluble diamine compound represented by the foregoing formula (2d), preferably the optically active water-soluble diamine compound represented by the foregoing formula (2e), which is the reaction substrate.

The amount of the solvent to be used is selected from the range of generally from 5 to 30 times, preferably from 10 to 20 times the volume of the water-soluble diamine compound as needed.

The reaction temperature is selected from the range of generally from 0 to 40°C, preferably from 0 to 10°C as needed.

The reaction time is selected from the range of generally from 2 to 10 hours, preferably from 3 to 5 hours as needed.

The obtained water-soluble diamine compound represented by the foregoing formula (2d), preferably optically active water-soluble diamine compound represented by the foregoing formula (2e) may be subjected to an aftertreatment, purification or the like as needed after the reaction. Specific methods and the like for the aftertreatment are as described above.

Thus obtained water-soluble diamine compound represented by the foregoing formula (2d) is useful as a ligand composing a transition metal complex or the like, and in particular, the optically active water-soluble diamine compound represented by the foregoing formula (2e) is useful as a ligand composing a transition metal complex used in asymmetric synthesis, an optical resolving agent or the like.

The water-soluble transition metal-diamine complex represented by the foregoing formula (1) of the present invention, preferably the optically active water-soluble transition metal-diamine complex represented by the foregoing formula (la) can be produced by the method described in Angewandt Chemie, Int. Ed. Engl., 36, No.

3,286 (1997) or the like, and for example, it can be produced as described below.

That is, it can be obtained by reacting the water-soluble diamine compound represented by the foregoing formula (2), preferably the water-soluble diamine compound represented by the foregoing formula (2a) with, for example, the transition metal compound represented by the foregoing formula (3) in accordance with the usual method.

In addition, in the case of using the transition metal compound in which n is 0 in the foregoing formula (3), it can be obtained by reacting the foregoing water-soluble diamine compound, the foregoing transition metal compound and a neutral ligand in accordance with the usual method. Herein, the transition metal compound in which n is 0 in the foregoing formula (3) may be a hydrate.

The amount of the transition metal compound represented by the formula (3) to be used is selected from the range of generally from 0.1 to 1.0 equivalent amount, preferably from 0.2 to 0.5 equivalent amounts relative to the foregoing water-soluble diamine compound as needed.

It is preferred that the production of the water-soluble transition metal-diamine complex be carried out in the presence of a solvent. Examples of the solvent include, for example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride and o-dichlorobenzene, alcohols such as methanol, ethanol, 2-propanol, n-butanol, 2-ethoxyethanol and benzylalcohol, and the like. These solvents may be used alone or in combination of two or more as needed.

The amount of the solvent to be used is selected from the range of generally from 10 to 40 times, preferably from 10 to 20 times the volume of the water-soluble diamine compound as needed.

The production of the water-soluble transition metal-diamine complex can be carried out in the presence of a base as needed. As the base, an organic base is preferred, and specific examples include organic amines such as triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine, 1, 5-diazabicyclo [4.3. 0] non-5-ene, 1, 8-diazabicyclo [5.4. 0] undec-7-ene, tri-n-butylamine, tetramethylethylenediamine, and N-methylmorpholine, alkali or alkaline earth metal alkoxides such as potassium methoxide, sodium methoxide, lithium methoxide, sodium ethoxide, potassium isopropoxide, potassium tert-butoxide, potassium naphthalenide, and the like.

The amount of the base to be used is selected from the range of generally from 0.5 to 5 equivalent amounts, preferably from 1 to 3 equivalent amounts relative to the water-soluble diamine compound as needed.

The reaction temperature is not particularly limited because it varies depending on, for example, the type of the water-soluble diamine compound, transition metal compound or the like, however, it is selected from the range of generally from 0 to 100°C, preferably from 20 to 80°C as needed.

The reaction time is not particularly limited because it varies depending on, for example, the reaction temperature, the type of the water-soluble diamine compound, the transition metal compound or the like, however, it is selected from the range of generally from 1 to 24 hours, preferably from 1 to 8 hours as needed.

Thus obtained water-soluble transition metal-diamine complex represented by the foregoing formula (1) of the present invention is useful as a catalyst for organic synthetic reaction or the like. In particular, the optically active water-soluble transition metal-diamine complex represented by the foregoing formula (la) is useful as, for example, a catalyst for asymmetric synthesis or the like, especially as an asymmetric hydrogenation catalyst or the like.

With regard to the water-soluble transition metal-diamine complex represented by the foregoing formula (la) of the present invention, for example, as described in Angewandt Chemie, Int. Ed. Engl. , 36, No. 3,288 (1997) or Angewandt Chemie, Int. Ed.

Engl., 36, No. 3,286 (1997), in the case of using the water-soluble transition metal-diamine complex represented by the foregoing formula (la) as, for example, an asymmetric hydrogenation catalyst, the water-soluble transition metal-diamine complex becomes a water-soluble transition metal-diamine-hydrido complex represented by the following formula (1-1), preferably an optically active water-soluble transition metal-diamine-hydrido complex represented by the following formula (la-1) during asymmetric hydrogenation. In addition, after finishing the asymmetric hydrogenation, the water-soluble transition metal-diamine complex becomes a water-soluble transition metal-amide complex represented by the following formula (1-2), preferably an optically active water-soluble transition metal-amide complex represented by the following formula (la-2). These water-soluble transition metal-diamine-hydrido complexes and water-soluble transition metal-amide complexes are also included within the scope of the water-soluble transition metal-diamine complex of the present invention.

(In the above formulae, Rl to R12, M, X, L and * are the same as above.) Next, the method for producing the optically active alcohol of the present invention will be explained.

The present invention provides a method for selective production of an optically active alcohols, which comprises hydrogenation of ketones with hydrogen resource, for example, hydrogen gas or hydrogen donor, in aqueous solvents in the presence of the chiral catalyst of the invention. The method of hydrogenation of this invention consists of a method of catalytic hydrogenation with hydrogen gas and of a method of transfer hydrogenation with hydrogen donor. Any ketones could be reduced by this method.

However, non-symmetrical ketones are desirable for the selective production of an optically active alcohols. Non-symmetrical ketones of this invention are defined that the ketones do not have a plane of symmetry on the carbonyl group, for example, two groups connected with the carbonyl group of the ketone are different. Favorable ketones of this method may be represented by the following formula (4): (wherein R21 and R22 are different groups, and R2l and R22 each independently represent a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent or a ferrocenyl group (provided that Ruz and R22 are not identical), or Ruz and R22 may be bound to each other to form a ring together with the carbon atom of the carbonyl group).

In the formula (4), the hydrocarbon group which may have a substituent represented by R2l and R22 represents a hydrocarbon group and a substituted hydrocarbon group, and the heterocyclic group which may have a substituent represents a heterocyclic group and a substituted heterocyclic group. The hydrocarbon group and the heterocyclic group are the same as the respective groups explained in the foregoing formula (1).

Examples of the substituted hydrocarbon group (hydrocarbon group having a substituent) include a hydrocarbon group in which at least one hydrogen atom of the foregoing hydrocarbon group was substituted by a substituent. Examples of the substituted hydrocarbon group include a substituted alkyl group, substituted aryl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group and the like.

Examples of the substituted heterocyclic group (heterocyclic group having a substituent) include a heterocyclic group in which at least one hydrogen atom of the foregoing heterocyclic group was substituted by a substituent. Examples of the substituted heterocyclic group include a substituted aliphatic heterocyclic group, substituted aromatic heterocyclic group and the like.

Examples of the substituent for the substituted hydrocarbon group and the substituted heterocyclic group include a hydrocarbon group, a heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an acyl group, an acyloxy group, an alkylthio group, an aralkylthio group, an arylthio group, a halogen atom, a halogenated hydrocarbon group, an alkylenedioxy group, an amino group, a substituted amino group, a cyano group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, a sulfonyl group, a substituted silyl group and the like.

The hydrocarbon group and the heterocyclic group as the substituent are the same as the respective groups explained in the foregoing formula (1). In addition, the halogen atom, the halogenated hydrocarbon group, the alkoxy group, the aryloxy group, the aralkyloxy group and the substituted amino group are the same as the respective groups explained as the substituent in the foregoing formula (1). The acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, and sulfonyl group are the same as the respective groups explained as the substituent for the amino group in the substituted amino group as the substituent in the foregoing formula (1).

Examples of the acyloxy group as the substituent include, for example, an acyloxy group having 2 to 18 carbon atoms derived from a carboxylic acid such as an aliphatic carboxylic acid or an aromatic carboxylic acid, and specific examples include, for example, acetyloxy, propionyloxy, butyryloxy, pivaloyloxy, pentanoyloxy, hexanoyloxy, lauroyloxy, stearoyloxy, benzoyloxy and the like.

The alkylthio group may be linear, branched or cyclic, and examples include, for example, an alkylthio group having 1 to 6 carbon atoms. Specific examples include, for example, methylthio, ethylthio, n-propylthio, 2-propylthio, n-butylthio, 2-butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio, cyclohexylthio and the like.

Examples of the arylthio group include, for example, an arylthio group having 6 to 14 carbon atoms, and specific examples include, for example, phenylthio, naphthylthio and the like.

Examples of the aralkylthio group include, for example, an aralkylthio group having 7 to 15 carbon atoms, and specific examples include, for example, benzylthio, 2-phenethylthio and the like.

In the case where the substituent is an alkylenedioxy group, adjacent two hydrogen atoms in the aromatic ring in, for example, the foregoing aryl group or aralkyl group are substituted by an alkylenedioxy group. Examples of the alkylenedioxy group include, for example, an alkylenedioxy group having 1 to 3 carbon atoms, and specific examples thereof include methylenedioxy, ethylenedioxy, trimethylenedioxy, propylenedioxy and the like.

Examples of the substituted silyl group include, for example, a trisubstituted silyl group in which three hydrogen atoms of a silyl group were substituted by a substituent such as the alkyl group, aryl group or aralkyl group described above.

Specific examples include, for example, trimethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, triphenylsilyl and the like.

In addition, such a substituent may be further substituted by the foregoing substituent.

Further, in the case where R ? l and R ? 2 were bound to each other to form a ring together with the carbon atom of the carbonyl group in the formula (4), the ring may be any of a monocyclic ring, polycyclic ring or condensed ring, and examples include, for example, 4-to 8-membered ring and the like. In addition,-O-,-NH-or the like may be included in the carbon chain constituting the ring. Specific examples of the ring in the case where Wl and R22 were bound to each other to form a ring together with the carbon atom of the carbonyl group include a cyclopentanone ring, a cyclohexanone ring, for example a 5-to 7-membered lactone ring, for example a 5-to 7-membered lactam ring and the like. When the cyclic ketone represented by the formula (4) which has no plane of symmetry, such a ring to be formed may be any ring in which the carbon atom of the carbonyl group in the formula (4) can become an asymmetric carbon by asymmetric hydrogenation.

The ketone represented by the formula (4) may be any ketone as long as it is a prochiral ketone. Specific examples of the ketone represented by the formula (4) include, for example, methyl ethyl ketone, acetophenone, benzalacetone, 1-indanone, 3, 4-dihydro- (2H)-naphthalenon ferrocenyl methyl ketone, and for example, the compounds shown below and the like.

Specific examples of the optically active alcohol represented by the formula (5) obtained by the production method of the present invention include 2-butanol, phenethyl alcohol and the like.

Above mentioned ketones will produce corresponding alcohols by the method of this invention. For example, ketons represented by the formula (4) produces optically active alcohols represented by the following formula (5): (wherein * represents an asymmetric carbon, and Ruz and R ? 2 are the same as above).

The method for producing the optically active secondary alcohol of the present invention, specifically, the asymmetric hydrogenation, more specifically, the asymmetric hydrogenation with hydrogen gas or the asymmetric transfer hydrogenation with hydrogen donor of the ketone represented by the foregoing formula (4) can be carried out by a known method, and is carried out in the presence of the chiral catalyst used in the present invention.

Examples of the chiral catalyst of the present invention include chiral catalyst comprising the optically active water-soluble transition metal-diamine complex represented by the foregoing formula (la) produced as described above, or/and chiral catalyst comprising the optically active water-soluble diamine compound represented by the foregoing formula (2c) and the transition metal compound represented by the foregoing formula (3).

The asymmetric hydrogenation using the latter chiral catalyst is a reaction that is carried out so-called in situ.

The asymmetric hydrogenation, in the case where it is carried out by using the optically active water-soluble transition metal-diamine complex represented by the foregoing formula (la), can be carried out by, for example, the method described in aforementioned Angewandt Chemie, Int. Ed. Engl. , 36, No. 3,286 (1997).

In addition, in the case where the asymmetric hydrogenation is carried out in situ by using the chiral catalyst comprising the optically active water-soluble diamine compound represented by the foregoing formula (2c) and the transition metal compound represented by the foregoing formula (3), the reaction can be carried out by, for example, the method described in aforementioned J. Am. Chem. Soc. , Vol. 118,4916-4917 (1996).

In the case where the asymmetric hydrogenation is carried out in situ, reaction mixture which has been heated and stirred for 1 to several hours in advance may be used.

The amount of the chiral catalyst to be used is selected from the range of generally from 10-1 to 10-4 equivalent amounts, preferably from 10-2 to 10 3 equivalent amounts relative to the ketone as needed.

Another method for producing the optically active secondary alcohol of the present invention, more specifically, the asymmetric hydrogenation of the ketone represented by the foregoing formula (4) is a method of transfer hydrogenation.

In the asymmetric hydrogenation by transfer hydrogenation, it is preferred that a hydrogen donor be present in the reaction system. The hydrogen donor may be an organic compound or/and an inorganic compound, and any can be used as long as it is a compound capable of donating hydrogen in the reaction by, for example, thermally or catalytically.

Examples of the hydrogen donor include, for example, formic acid, a salt thereof, the combination of formic acid and a base, hydroquinone, phosphorous acid, an alcohol and the like. Among these, formic acid, a salt thereof, the one consisting of the combination of formic acid and a base, an alcohol and the like are particularly preferred.

With regard to the formic acid and the salt thereof, examples of the salt of formic acid include metal salts of formic acid such as an alkali metal salt and an alkaline earth metal salt of formic acid, an ammonium salt, substituted amine salt and the like.

In addition, it may be the one that becomes a form of formate or the one that substantially becomes a form of formate in the reaction of combination of formic acid and a base.

Examples of the alkali metal that forms the salt together with formic acid include lithium, sodium, potassium, rubidium, caesium and the like. In addition, examples of the alkaline earth metal include magnesium, calcium, strontium, barium and the like.

Examples of the base for forming these metal salts of formic acid such as an alkali metal salt and an alkaline earth metal salt of formic acid, ammonium salt, substituted amine salt and the like, and the base in the combination of formic acid and a base include ammonia, an inorganic base, an organic base and the like.

Examples of the inorganic base include, for example, salts of an alkali metal or an alkaline earth metal such as potassium carbonate, potassium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, sodium hydroxide, magnesium carbonate, calcium carbonate and the like, and metal hydrides such as sodium hydride, sodium borohydride, aluminium lithium hydride and the like.

Examples of the organic base include, for example, alkali metal alkoxides such as potassium methoxide, sodium methoxide, lithium methoxide, sodium ethoxide, potassium isopropoxide, potassium tert-butoxide, potassium naphthalenide and the like, and salts of an alkali metal or an alkaline earth metal such as sodium acetate, potassium acetate, magnesium acetate and calcium acetate, organic amines such as triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine, 1, 5-diazabicyclo [4.3. 0] non-5-ene, 1, 8-diazabicyclo [5.4. 0] undec-7-ene, tri-n-butylamine and N-methylmorpholine, organic metal compounds such as magnesium methyl bromide, magnesium ethyl bromide, magnesium propyl bromide, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium and tert-butyl lithium, quaternary ammonium salt and the like.

With regard to the alcohol as the hydrogen donating substance, a lower alcohol having a hydrogen atom at the a-position is preferred. Specific examples include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and the like.

Among them, isopropanol is preferred.

In the method for producing the optically active secondary alcohol of the present invention, since the asymmetric hydrogenation is carried out in an aqueous solvent which is described below as the solvent, as the hydrogen donating substance to be used, the one which is soluble in water is preferred, and examples include, in particular considering the reactivity and economic efficiency, an alkali metal salt, alkaline earth metal salt, anmonium salt and substituted amine salt of formic acid and the like.

The amount of the hydrogen donating substance to be used is selected from the range of generally from 2 to 20 equivalent amounts, preferably from 4 to 10 equivalent amounts relative to the ketone as needed. After the reaction, when the aqueous phase remaining after separating the product is reused, the formate of the hydrogen source consumed in the reaction may be replenished.

It is preferred that the method for producing the optically active secondary alcohol of the present invention be carried out by using water as the solvent. By carrying out the reaction in an aqueous solvent, the aqueous phase containing the produced secondary alcohol and the water-soluble transition metal-amide complex can be easily separated, and further the separated aqueous phase containing the water-soluble transition metal-amide complex can be used repeatedly, in other words, recycle (reuse) thereof becomes possible.

The amount of water to be used is selected considering the type or solubility of the ketone, which is the reaction substrate, economic efficiency or the like, however, it is selected from the range of generally from 5 to 50 times, preferably from 10 to 40 times the mass of the substrate as needed.

In addition, in the method for producing the optically active secondary alcohol of the present invention, based on the type of the ketone to be used, water and an organic solvent may be used in combination as needed.

Examples of the organic solvent to be used include, for example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane and octane, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and dichloroethane, ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether, dimethoxyethane, tetrahydrofuran, dioxane and dioxolane, alcohols such as methanol, ethanol, 2-propanol, n-butanol, tert-butanol and benzylalcohol, polyhydric alcohols such as ethylene glycol, propylene glycol, 1,2-propanediol and glycerin, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, acetonitrile, N-methylpyrrolidone, dimethylsulfoxide and the like. These solvents may be used alone or in combination of two or more as needed.

The amount of the organic solvent to be used is selected from the range of generally from 1 to 10 times, preferably from 2 to 5 times the volume of the ketone to be used as needed.

The reaction temperature is selected from the range of generally from 15 to 100°C, preferably from 20 to 80°C as needed considering the economic efficiency, and it is desired that the reaction be generally carried out at a relatively low temperature.

The reaction time varies depending on the type or the amount of the asymmetric hydrogenation catalyst to be used, the type or the concentration of the ketone compound to be used, the reaction conditions such as reaction temperature, etc. However, it may be about several minutes to several tens hours, and is selected from the range of generally from 4 to 48 hours, preferably from 6 to 24 hours as needed.

The method for producing the optically active alcohol of the present invention can be carried out either batchwise or continuously with respect to the reaction system.

In the production method of the present invention, the aqueous solution containing the chiral catalyst used in the previous asymmetric hydrogenation can be recovered for use. That is, in the production method of the present invention, recycle (reuse, reutilize) of the chiral catalyst is possible.

The chiral catalyst and the aqueous solution thereof can be recovered from the reaction solution (reaction system) by adopting the usual procedure.

More specifically, after finishing the hydrogenation, if necessary an organic solvent or water is added to the reaction solution to make a two-phase solution, and by separating the aqueous phase from this two-phase reaction solution, the aqueous solution containing the chiral catalyst can be recovered.

The recovered aqueous solution (aqueous phase separated after the hydrogenation) containing the chiral catalyst can be directly reused (recycled) in the asymmetric hydrogenation of the ketone without performing an aftertreatment, purification or the like.

In addition, if necessary, the chiral catalyst can be easily recovered from this separated aqueous phase by a procedure such as concentration.

As the organic solvent to be used as needed when separating the aqueous phase after finishing the hydrogenation, any can be used as long as it is phase-separated from water. Specific examples thereof include, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether, dimethoxyethane, ethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane and 1,3-dioxolane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride and o-dichlorobenzene, esters such as methyl acetate, ethyl acetate, n-butyl acetate and methyl propionate and the like.

These organic solvents may be used alone or in combination of 2 or more as needed.

On the other hand, the isolated and recovered chiral catalyst can be reused in the asymmetric hydrogenation of the ketone after performing an aftertreatment, purification or the like, however, it can be used in another asymmetric hydrogenation.

In the case where reuse (recycle) is carried out in the hydrogenation of the ketone by using the recovered chiral catalyst, in other words, the aqueous phase containing the chiral catalyst recovered from the reaction solution (reaction system) or the chiral catalyst subjected to isolation or the like, the amount of the chiral catalyst may be optionally adjusted by adding fresh chiral catalysts or the like as needed.

Thus obtained optically active secondary alcohol is useful as a pharmaceutical intermediate, a liquid crystal material or the like.

Hereunder, the present invention will be explained in more detail with reference to the Examples, however, the present invention is not intended to be limited by these Examples.

Incidentally, in the following Examples, the apparatus used for the measurement of physical property or the like is as follows.

1) Gas chromatography (GLC): i) Column TC-WAX ii) Column Chiraldex G-PN 2) Specific optical rotation: Nippon Bunko JASCO DIP-360 type polarimeter 3) 1H-NMR, 13C-NMR : Model number DRX-500, by BURUKER Co.

5) HPLC: Column Hypersil SAS (Cl) [Example 1] Synthesis of (1R, 2R)-diphenylethylene-1, 2-diamine monobenzenesulfamide Under nitrogen atmosphere, 5 mL of a dichloromethane solution containing 3 g of benzenesulfonyl chloride (14.1 mmol) was added dropwise over 2 hours to a solution consisting of 2.5 g of (1R, 2R)-diphenylethylene-1, 2-diamine (14.2 mmol), 1.72 g of triethylamine (17 mmol) and 10 mL of dichloromethane, while the temperature of the solution was kept at 10°C or lower. A cooling bath was removed and the reaction was continued with stirring for an additional 3 hours, then the solution was left undisturbed overnight. The solvent was recovered and 5.82 g of a solid substance of crude (1R, 2R)-diphenylethylene-1, 2-diamine monobenzenesulfamide was obtained. This was ground in 40 mL of ethyl acetate and an insoluble substance was removed by filtering.

The dry weight of the insoluble substance was 1.38 g. In silica gel TLC (ethyl acetate), three spots of raw material (the original spot), (1R, 2R)-diphenylethylene-1, 2-diamine monosulfamide and disulfamide were detected.

The ethyl acetate solution of (1R, 2R)-diphenylethylene-1, 2-diamine monobenzenesulfamide, which was the filtrate, was directly applied to silica gel column chromatography (ethyl acetate) for purification. Thus, 2.76 g of purified (1R, 2R)-diphenylethylene-1, 2-diamine monobenzenesulfamide (white powder) was obtained.

Yield: 55. 5%. (HPLC: 98. 3%) lH-NMR (MeOH) 8 : 3.99 (1H, d, 8.8 Hz), 4.41 (1H, d, 8.8 Hz), 6.7 (2H, d, 7.5 Hz), 6.9 (3H, m), 7.08 (5H, m), 7.2 (2H, t, 7.5 Hz), 7.33 (1H, t, 7.5 Hz), 7.49 (2H, d, 8.1 Hz) ppm.

3C-NMR (MeOH) 8 : 62.3, 66.7, 127.8, 127.9, 128,128. 4,128. 5,128. 6,128. 7,128. 8, 129.2, 129.6, 133,139. 7,142 ppm.

[Example 2] Synthesis of (1R, 2R) -di (3,3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine A 50-mL reaction container replaced with nitrogen atmosphere was used for reactions. (1R, 2R)-diphenylethylene-1, 2-diamine monobenzenesulfamide (1.59 g: 4.54 mmol) was added over about 5 minutes to the mixed solution consisting of 11.1 g of concentrated sulfuric acid (113.57 mmol) and 22.8 g of 30% fuming sulfuric acid (30% SO3-H2SO4) (SO3 = 85.5 mmol) chilled to 0°C. After stirring for 6 hours at 5°C or lower, a cooling bath was removed and the solution was left undisturbed for 4 days. The reaction solution was carefully quenched on 500 g of crushed ice, neutralized with 50% sodium hydroxide aqueous solution, and further alkalized. This aqueous solution was concentrated by distillation and 80.8 g of a block-like white solid substance was obtained.

In order to remove sodium sulfate contained in the concentrated substance, after the block-like white solid substance was crushed, 150 mL of 10% aqueous methanol was added and the solution was heated to reflux for 30 minutes. This was filtered while it was hot and sodium sulfate (dry weight: 79.5 g) was separated. The filtrate was concentrated under reduced pressure, then, dried under high vacuum, whereby 4.24 g of a solid substance was obtained. This solid substance was again heated to reflux in 14.4 mL of 10% aqueous methanol for 30 minuets. After the solution was cooled down to room temperature, it was filtrated. After the filtrate was concentrated, it was dried under high vacuum and 2.2 g of a grayish white solid substance was obtained.

By'H-NMR, it was confirmed that this grayish white solid substance is (1R, 2R) -di (3, 3'-sodium oxysulfonyl-phenyl) ethylene-1,2-diamine.

The analysis values are as follows.

[a] D20=-80. 2 (c = 1, H20).

1H-NMR (CD30D) 8 : 4.37 (2H, s), 7.18 (2H, dt, 7.7 Hz, 1 to 3 Hz, the protons at the 6- and 6'-positions of the phenyl group), 7.32 (2H, t, 7.7 Hz, the protons at the 5-and 5'- positions of the phenyl group), 7.65 to 7.68 (4H, m, the protons at the 2-and 2'-positions, and the 4-and 4'-positions of the phenyl group) ppm.

3C-NMR (CD30D) 8 : 59.8, 124.4, 126.1, 130,131. 2,138. 4,143. 5 ppm The structure of this solid product was determined as (1R, 2R) -di (3, 3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine by NMR spectrum (in deuterium oxide) and mass spectrum (ESI method).

NMR: 13C-NMR ; the signals of5= 143.5, 138.4 ppm are attributed to the carbon atoms at the 3-and 3'-positions of the benzene ring to which S03Na was bound, those of 131.2, 130,126. 4 and 124.4 ppm are attributed to the carbon atoms in the benzene ring and that of 59.9 ppm is attributed to the carbon atom of 1,2-diaminoethylene, respectively.

ESI mass spectrum (m/z) ; ESI+: 417 (M+1), 439 (M+Na), 395 (M-Na) and 812, 834 and 856 derived from the cluster of two molecules. ESI- : 393 (M-23), 371 (M-2Na) and 765,787 and 809 derived from the cluster of two molecules.

1H-NMR (500 MHz, D2O, ppm, Hz): 4.37 (2H, s, the protons at the 1-and 2-positions of ethylene), 7.18 (2H, dt, 7.7Hz, 1 to 3 Hz, the protons at the 6-and 6'-positions of the phenyl group), 7.32 (2H, t, 7.7Hz, the protons at the 5-and 5'-positions of the phenyl group), 7.63 to 7.68 (4H, m, the protons at the 2-and 2'-positions, and the 4-and 4'-positions of the phenyl group). Since there are substituents at the 1-and 3-positions, J-value for the proton at the 2-position (this applies also to the 2'-position) of the phenyl group is different from those for the protons at other positions. That is, J-value between the protons at the 2-position and at the 4-or 5-position of 0.9 to 2 Hz, which is small, is detected. On the contrary, the J-values for the adjacent protons at the 4-and 5-positions, and the 5-and 6-positions are 7.7 Hz, respectively.

[Example 3] Asymmetric transfer hydrogenation of acetophenone using (1R, 2R) -di (3, 3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine, [RhCl2 (pentamethyl cyclopentadiene)] 2 (hereinafter abbreviated as [Cp*RhCl2] 2) and ammonium formate Under nitrogen atmosphere, a solution consisting of 4.4 mg of (1R, 2R) -di (3, 3'-sodium oxysulfonyl-phenyl) ethylene-1, 2-diamine (0.0105 mmol), 2.57 mg of [Cp*RhCl2] 2 (0.0041 mmol), 0.2 g of acetophenone (1.66 mmol), 0.42 g of ammonium formate (6.7 mmol) and 4 mL of water was stirred at 80°C for 20 hours for reaction.

The organic layer was extracted with diisopropyl ether, dried with anhydrous magnesium sulfate, and concentrated, whereby crude optically active (lR)-phenethyl alcohol was obtained. GC: conversion rate: 99.3%, selectivity: 99.8%, optical purity: 60.2% ee.

[Example 4] Asymmetric transfer hydrogenation of acetophenone using (1R, 2R) -di (3,3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine, [Cp*IrCl2] 2 and ammonium formate Asymmetric transfer hydrogenation of acetophenone was carried out in the same manner as in the Example 3 except that the metal complex, [IrCl2 (pentamethyl cyclopentadiene)] 2 (hereinafter abbreviated as [Cp*IrCl2] 2) was used and the reaction time was set to 18 hours, whereby crude optically active (lR)-phenethyl alcohol was obtained. GC: conversion rate: 73. 4%, selectivity: 99.8%, optical purity: 58% ee.

[Example 5] Asymmetric transfer hydrogenation of acetophenone using (1R, 2R) -di (3,3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine, [Cp*RhCl2] 2 and sodium formate Under nitrogen atmosphere, a solution consisting of 6.5 mg of (1R, 2R) -di (3, 3'-sodium oxysulfonyl-phenyl) ethylene-1, 2-diamine (1.66 mmol), 5.13 mg of [Cp*RhCl2] 2 (0.0082 mmol), 0.2 g of acetophenone (1.66 mmol), 0.46 g of sodium formate (6.7 mmol) and 4 mL of water was stirred at 50°C for 3 hours for reaction. The organic layer was extracted with diisopropyl ether, dried with anhydrous magnesium sulfate, and concentrated, whereby crude optically active (lR)-phenethyl alcohol was obtained. GC: conversion rate: 98.8%, selectivity: 99.4%, optical purity: 64.9% ee.

[Example 6] Asymmetric transfer hydrogenation of acetophenone using (1R, 2R) -di (3, 3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine, [Cp*IrCl2] 2 and sodium formate Asymmetric transfer hydrogenation of acetophenone was carried out in the same manner as in the Example 5 except that the metal complex, [Cp*IrCl2] 2 was used and the reaction time was set to 22 hours, whereby crude optically active (lR)-phenethyl alcohol was obtained. GC: conversion rate: 94.4%, selectivity: 99.8%, optical purity: 68.2% ee.

[Example 7] Synthesis of benzenesulfamide of (1R, 2R) -di (3,3'-sodium oxysulfonylphenyl) ethylene-1,2-diamine Under nitrogen atmosphere, a solution consisting of 0.5 g of (1R, 2R) -di (3, 3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine (1.2 mmol), 0.242 g of triethylamine (2.4 mmol) and 10 mL of DMF was chilled to 5°C or lower. To this solution, 2.5 mL of DMF solution-containing 0.2545 g of benzenesulfonyl chloride (1.44 mmol) was added dropwise over 3 hours, while the temperature of the solution was kept at 5°C or lower. At the same temperature, the solution was stirred for an additional 2.5 hours for reaction, and then it was left undisturbed overnight. The DMF in the reaction solution was recovered by distillation, whereby 0.75 g of crude benzenesulfamide of (1R, 2R) -di (3, 3'-sodium oxysulfonyl-phenyl) ethylene-1, 2-diamine was obtained.

The composition of the product by HPLC: monobenzenesulfamide of (1R, 2R) -di (3,3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine: 52.8%, dibenzenesulfamide : 5.5% and unreacted (1R, 2R) -di (3,3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine: 1. 8%.

[Example 8] Asymmetric transfer hydrogenation of acetophenone using crude benzenesulfamide of (1R, 2R) -di (3,3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine and [Cp*RhC12] 2 The crude benzenesulfamide of 7.5 mg of (1R, 2R) -di (3,3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine (0.0166 mmol), 2.47 mg of [Cp*RhCl2] 2 (0.0083 mmol), 0.2 g of acetophenone (1.66 mmol), 4 mL of water and 0.92 g of sodium formate (13.4 mmol) were mixed and stirred at 80°C for 17 hours for reaction. The product was extracted with diisopropyl alcohol, dried with anhydrous magnesium sulfate, and concentrated, whereby crude (lR)-phenethyl alcohol was obtained. GC: conversion rate: 99.3%, selectivity: 99.9%, optical purity: 52.9% ee.

[Example 9] Asymmetric transfer hydrogenation of acetophenone using crude benzenesulfamide of (1R, 2R) -di (3,3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine and [RuI2 (p-cymene)] 2 A solution consisting of 7.5 mg of the crude benzenesulfamide of (1R, 2R) -di (3, 3'-sodium oxysulfonylphenyl) ethylene-1, 2-diamine (0.0166 mmol), 4.1 mg of [RuI2 (p-cymene)] 2 (0.0083 mmol), 0.2 g of acetophenone (1.66 mmol) and 4 mL of water was stirred at 50°C for 1.5 hours for reaction, 0.92 g of sodium formate (13.4 mmol) was added and stirred at the same temperature for 6 hours for reaction. The product was extracted with n-hexane, dried with anhydrous magnesium sulfate, and concentrated, whereby crude (IS)-phenethyl alcohol was obtained. GC: conversion rate: 95.8%, selectivity: 99.8%, optical purity: 91.7% ee.

[Example 10] Reuse (recycle) of chiral catalyst used in asymmetric transfer hydrogenation To the aqueous phase after the product was extracted with diisopropyl alcohol after the reaction in the Example 8,0. 2 g of acetophenone (1.66 mmol) was added and stirred at 80°C for 12 hours for reaction. After the reaction, by treating the solution in the same manner as in the Example 8, crude (lR)-phenethyl alcohol was obtained.

Conversion rate: 95.6%, selectivity: 99.8%, optical purity: 91.7% ee.

Industrial Applicability The optically active water-soluble transition metal-diamine complex of the present invention is useful as a catalyst for various organic synthetic reactions, particularly for asymmetric transfer hydrogenation or the like, and it can be effectively used in the production of an optically active secondary alcohol that is useful as a pharmaceutical intermediate, a liquid crystal material or the like. In addition, the complex catalyst of the present invention can be recycled, therefore the cost can be reduced. Further, asymmetric hydrogenation can be carried out in an aqueous solvent, therefore, asymmetric hydrogenation considering the environmental aspect is possible, and contribution to this industry is extremely large.