Catalyst comprising activated carbon adsorbed with a ruthenium complex and method for producing a reduction product using the same

Abstract

The object of the present invention is to provide a catalyst that exhibits high reusability and can also reduce the amount of residual metal in the reaction solution in a method for producing an optically active reduction product by a sub-reduction reaction of an organic compound. The present invention relates to a catalyst comprising activated carbon adsorbed with a ruthenium complex represented by the following general formulas (1-1) and / or (1-2). (In the formula, j, k, X, Y, and R1 to R10 are as defined in Claim 1.)

Description

Technology Field

[0001] The present invention relates to a catalyst comprising activated carbon adsorbed with a novel ruthenium complex and a method for producing a reduced product comprising a process for reducing an organic compound using the same. Background Technology

[0002] It has been reported numerous times that ruthenium complexes having optically active diamines as ligands exhibit excellent performance as homogeneous catalysts for auxiliary reduction reactions. For example, using these catalysts enables the efficient production of optically active alcohols by auxiliary reduction of ketones and imines using molecular hydrogen, formic acid, or formate as the hydrogen source. Among these, various optically active diamine ligands have been developed to enhance the performance of the catalyst (see Patent Documents 1, 2, and 3 and Non-Patent Documents 1 and 2).

[0003] Many methods are being employed to immobilize such ruthenium complexes on solid supports to function as heterogeneous catalysts. Complexes supported on solid supports can impart characteristics not found in homogeneous catalysts, such as the ability to reuse the catalyst or reduce the amount of dissolved metal remaining after the reaction; this is expected to lead to the resolution of important challenges, such as the reduction of environmental burden and the improvement of manufacturing costs.

[0004] As a method for immobilizing ruthenium complexes for sub-reduction, a method of crosslinking functional groups on the surface of a ligand and a carrier is being investigated, and it has been found that loading onto silica (see Patent Document 4 and Non-Patent Document 3) or various polymers (see Non-Patent Document 4) is effective.

[0005] In addition, a method has been reported in which the ligand of the complex is immobilized without cross-linking the surface of the carrier by chemically modifying the pores of a specific carrier (see Non-Patent Literature 5).

[0006] The aforementioned support method has limited industrial applicability because it requires the novel chemical modification of conventional ruthenium complexes or catalyst supports, which leads to increased costs for the production of the desired optically active alcohol. Furthermore, depending on the catalyst or reaction substrate used, a decrease in catalyst efficiency or byproduct yield may be observed due to immobilization on the support.

[0007] As a supporting example that does not require chemical modification of the complex and the support, it is known that activated carbon is used as the support, and activated carbon supported catalysts obtained by supporting RuCl2(PPh3)3 complex or [RuCl(p-cymen)]2 complex are reported to be useful for the oxidation reaction of alcohols and diols (see Non-Patent Literature 6, 7).

[0008] Meanwhile, there are no synthetic examples of activated carbon-supported complexes useful for the reduction of ketones, and carbon material-supported ruthenium catalysts effective for the reduction of ketones are limited to examples of activated carbon-supported ruthenium nanoparticle catalysts that impart racemic alcohols (see Non-Patent Literature 8). Prior art literature

[0009] Japanese Patent No. 3040353, Japanese Patent No. 5718178, Japanese Patent No. 5727127, International Publication No. 2016-056669

[0010] Acc. Chem. Res. 30 (1997) p. 97-102J. Am. Chem. Soc. 133 (2011) p. 14960-14963Org. Lett. 6 (2004) p. 169-172Tetrahedron Asymmetry 9 (1998) p. 2015-2018Chem. Commun. 46 (2010) p. 8145-8147Org. Lett. 1 (1999) p. 713-715Org. Lett. 4 (2002) p. 2369-2371Org. Process Res. Dev. 22 (2018) p. 1580-1585 The problem to be solved

[0011] The object of the present invention is to provide a catalyst capable of exhibiting high reusability and reducing the amount of residual metal in the reaction solution in a method for producing an optically active reduction product by a sub-reduction reaction of an organic compound. Furthermore, another object of the present invention is to provide said catalyst in a simple manner that does not require chemical modification of the complex and the support. means of solving the problem

[0012] In order to solve the above problem, as a result of repeated careful examinations regarding the loading of complexes onto a solid carrier, it was discovered that by using activated carbon as the carrier, a ruthenium complex having an optically active diamine as a ligand can be loaded using a simple method.

[0013] Furthermore, it was discovered that a catalyst comprising activated carbon adsorbed with a ruthenium complex according to the present invention provides catalytic efficiency comparable to that of a complex catalyst and an equivalent yield for the reduction reaction of ketones. The catalyst of the present invention also exhibits almost no metal leaching into the reaction solution. Additionally, it was discovered that there is almost no decrease in catalytic efficiency or yield in the reduction reaction even upon reuse, leading to the completion of the present invention.

[0014] That is, the present invention includes the following contents.

[0015] [1] A catalyst comprising activated carbon adsorbed with a ruthenium complex represented by the following general formulas (1-1) and / or (1-2).

[0016] [Chemical Formula 1]

[0017]

[0018] (among the above formulas,

[0019] Solid lines represent single bonds, double lines represent double bonds, and dashed lines represent coordinate bonds;

[0020] Ru represents a ruthenium atom, N represents a nitrogen atom, S represents a sulfur atom, and O represents an oxygen atom;

[0021] * indicates a carbon atom;

[0022] j and k are integers of 0 or 1, and j+k is not 1, X represents an anionic group, and Y represents a hydrogen atom;

[0023] R 1 1 to 10 carbon atom straight-chain or branched-chain alkyl group; 10-camparyl group; 1 to 10 carbon atom alkyl group, 1 to 10 carbon halogenated alkyl group, halogen atom, cyano group (-CN), amino group, alkylamino group (-NR 11 R 12 ), 5- or 6-membered cyclic amino group, acylamino group (-NH-CO-R 11 ), hydroxyl group, alkoxy group (-OR 11 ), acyl group(-CO-R 11 ), carboxyl group, alkoxycarbonyl group (-COOR 11 ), phenoxycarbonyl group, or alkylthio group (-SR 11 ) representing an aryl group that may be substituted; or an aralkyl group that may be substituted with an alkyl group having 1 to 10 carbon atoms;

[0024] R 11 and R 12 Each independently represents a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; or a cycloalkyl group having 3 to 10 carbon atoms;

[0025] R 2 and R 3 Each represents independently a hydrogen atom; or a phenyl group that may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, or

[0026] R 2 and R 3 They combine with each other to form R 2 and R 3Together with the bonded carbon atom, it forms a cycloalkane ring of 4 to 8 members;

[0027] R 4 represents a hydrogen atom; or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms that may have substituents;

[0028] R 5 to R 10 Each independently represents a hydrogen atom; a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; a hydroxyl group; or a straight-chain or branched-chain alkoxy group having 1 to 10 carbon atoms;

[0029] R 4 and R 5 They may combine with each other to form two cross-linked regions as shown in the following formula (W) to form a cross-linked region (W).

[0030] [Chemical Formula 2]

[0031]

[0032] (Equation (W),

[0033] n 1 The dashed line portion of the carbon chain end containing R in formulas (1-1) and (1-2) 5 Instead, it bonds to the carbon atom of the arene site, and n in formula (W) 2 The dashed line portion of the carbon chain end containing R in formulas (1-1) and (1-2) 4 Instead, it bonds with the nitrogen atom of the amine site;

[0034] Z represents a methylene group or an oxygen atom;

[0035] n 1 is an integer of 1 or 2;

[0036] n 2 is any integer from 1 to 3.))

[0037] [2] R 4 and R 5 They combine with each other to form a two-group cross-linking site represented by the above formula (W), and

[0038] Z is an oxygen atom, and

[0039] n 1 This is 1, and

[0040] n 2 2 people,

[0041] The catalyst described in [1] above.

[0042] [3] R 1 This is a 4-methylphenyl group or a methyl group, and

[0043] R 2 and R 3 This is a phenyl group, and

[0044] R 6 , R 7 , R 9 and R 10 This is a hydrogen atom, and

[0045] R 8 This methyl group,

[0046] The catalyst described in [2] above.

[0047] [4] R 4 and R 5 ga does not form a cross-linking site of the two groups represented by the above formula (W), and

[0048] R 4 a hydrogen atom,

[0049] The catalyst described in [1] above.

[0050] [5] R 1 This is a 4-methylphenyl group, a 2,3,4,5,6-pentafluorophenyl group, a methyl group, an isobutyl group, a benzyl group, a 2',5'-dimethylbenzyl group, or a 10-camparyl group, and

[0051] R 2 and R 3 These phenyl groups or bond with each other to form a cyclohexane ring,

[0052] R 5 , R 6 , R 7 , R8 , R 9 and R 10 The catalyst described in [4] above, which is a hydrogen atom, a methyl group, or an isopropyl group.

[0053] [6] A catalyst described in any one of [1] to [5], wherein the total mass of the ruthenium complex is 0.1 mass% or more and 25 mass% or less with respect to the total mass of the activated carbon.

[0054] [7] A catalyst described in any one of [1] to [6], wherein the specific surface area of ​​the activated carbon is 800 m² / g or more and 2000 m² / g or less.

[0055] [8] A method for producing a reduced product comprising a process of reducing an organic compound in the presence of a catalyst and a hydrogen donor as described in any one of [1] to [7] above.

[0056] [9]

[0057] A method for producing an optically active alcohol, comprising a process of reducing the carbonyl group of a carbonyl compound in the presence of a catalyst and a hydrogen donor as described in any one of [1] to [7] above.

[0058]

[10]

[0059] A method for producing an optically active amine, comprising a process of reducing the imino group of an imine compound in the presence of a catalyst and a hydrogen donor as described in any one of [1] to [7] above.

[0060]

[11] A method of manufacturing as described in any one of [8] to

[10] , wherein the hydrogen donor is at least one selected from the group consisting of formic acid, alkali metal salts of formic acid, alcohols having a hydrogen atom at the α-position carbon atom of a hydroxyl-substituted carbon, and hydrogen gas.

[0061] In addition, in the present invention, "adsorption" and "carrying" are used as synonyms. Effects of the invention

[0062] The present invention can provide a catalyst that exhibits high reusability and can also reduce the amount of residual metal in the reaction solution in a method for producing an optically active reduction product by an auxiliary reduction reaction of an organic compound. Furthermore, the present invention can provide said catalyst in a simple manner that does not require chemical modification of the complex and the support. Brief explanation of the drawing

[0063] Figure 1 is a graph showing the change in the conversion rate over time examined in Example 32. Figure 2 is a graph showing the change in conversion rate over time examined in Examples 32 and 33. Figure 3 shows the (R,R)-Ts-DENEB complex and π-conjugated compound in coexistence 1 This is a chart showing the analysis results of H NMR. Figure 4 shows SEM images of catalyst 17 and catalyst 19 and ruthenium element mapping images taken by SEM-EDS. Specific details for implementing the invention

[0064] [catalyst]

[0065] The catalyst of the present invention is characterized by comprising activated carbon, which is a carrier that adsorbs a tethered ruthenium complex and / or a non-tethered ruthenium complex represented by formulas (1-1) and / or (1-2) described below. The tethered ruthenium complex and / or non-tethered ruthenium complex used in the present invention will be described below, but these ruthenium complexes have a ligand with a benzene ring as the basic structure. In the catalyst according to the present invention, it is thought that the activated carbon and the ruthenium complex mutually adsorb through the interaction of the aromatic rings, particularly the benzene ring structures, that both possess. This is also supported by the result shown in FIG. 3, that is, when (R,R)-Ts-DENEB and the π-conjugated compound coexist, an interaction occurs between the aromatic ring on the ruthenium and the π-conjugated compound, causing the peak (4.5 ppm to 6.2 ppm) attributed to the protons around the aromatic ring on the ruthenium to shift toward the high magnetic field side.

[0066] In addition, regarding the catalyst of the present invention, although not particularly limited, it is preferable that the total mass of the ruthenium complex is in the range of 0.1 mass% to 25 mass% with respect to the total mass of the activated carbon, and it is preferable that it is in the range of 1 mass% to 10 mass%, as this allows the catalyst to perform its intended function while suppressing the ruthenium leaching amount from the catalyst of the present invention after the reaction, thereby increasing reusability. Furthermore, in the catalyst of the present invention, it is more preferable that the ruthenium complex is uniformly supported on the surface of the activated carbon or within it.

[0067] Here, in the present invention, the loading amount (or adsorption amount) of a complex relative to the total mass of activated carbon in the catalyst may be a value calculated from the amount of unadsorbed complex measured in the analysis during the manufacturing process as in the present embodiment, but as an objective value, a value calculated by the surface analysis of activated carbon by SEM-EDS as in Analysis 2 of the present embodiment may be adopted as the loading amount.

[0068] In the complex of the present invention, since chemical modifications for mutual bonding are unnecessary for both the ligand of the ruthenium complex and the activated carbon serving as the carrier, there is an advantage of easier synthesis compared to conventionally used ruthenium complexes, such as those supported on silica or polymers. Furthermore, the catalyst of the present invention includes activated carbon as a carrier, and since the ruthenium complex can be recovered while adsorbed onto the activated carbon, it has high reusability. Here, in the catalyst of the present invention, it is more preferable that the ruthenium complex be of the tether type. This is because the ruthenium complex tends to have high catalytic activity, as it has a covalent bond between the benzene ring portion and the diamine portion of the ruthenium, thereby suppressing the release of the ligand from the ruthenium.

[0069] By configuring the catalyst of the present invention, which includes a ruthenium complex adsorbed on activated carbon, the catalytic activity is enhanced, and when used, for example, in the production of chiral alcohols, the optical purity obtained tends to be improved. Furthermore, when the catalyst according to the present invention is contained in a highly polar solvent, such as water or ethanol, the bond between the activated carbon and the ruthenium complex tends to become stronger.

[0070] Hereinafter, the activated carbon and ruthenium complex constituting the catalyst according to the present invention will be described, and then a method for adsorbing the ruthenium complex onto the activated carbon will be described.

[0071] [Activated Carbon]

[0072] The specific surface area of ​​the activated carbon carrier in the present invention is generally 700 to 3000 m² / g, preferably 800 to 2000 m² / g, and more preferably 1200 to 1800 m² / g. The specific surface area of ​​the activated carbon used in the present invention affects the adsorption amount of the target complex. In the present invention, the specific surface area of ​​the activated carbon can be a value measured, for example, by the method specified in JIS Z8830:2013 (ISO9277:2010).

[0073] Since the average pore diameter of the adsorbent of the present invention affects the reaction activity of the catalyst, it is preferably 1.0 to 5.0 nm, and more preferably 1.5 to 4.0 nm. The average pore diameter of the adsorbent of the present invention is determined from the pore volume and specific surface area obtained from the amount of nitrogen adsorbed.

[0074] Activated carbon typically has acidic groups on its surface. The types of acidic groups on the surface of activated carbon vary depending on the activated carbon, but they can be evaluated by measuring the amount of acidic groups. Among these, since acidic groups affect the reactivity of the catalyst, there are no specific limitations, but it is desirable to have as little acidic content as possible, and specifically, it is desirable to have a low amount of acidic content in the activated carbon as measured by sodium hydroxide.

[0075] In the above view, in the adsorbent of the present invention, the acidity amount measured by sodium hydroxide is preferably 0.50 mmol / g or less, more preferably 0.20 mmol / g or less, and even more preferably 0.10 mmol / g or less.

[0076] The shape of the adsorbent of the present invention may be granular, powdered, or fibrous. That is, when the adsorbent of the present invention is composed of activated carbon, any of granular activated carbon, powdered activated carbon, or fibrous activated carbon may be used. Furthermore, granular activated carbon refers to activated carbon with a particle size of 0.150 mm or more as specified in JIS K1474. Here, a particle size of 0.150 mm or more as specified in JIS K1474 is equivalent to a particle size of 0.150 mm or more as measured by the specifications of JIS K1474, and specifically, the sample having a particle size range of 0.150 mm or more has a mass fraction of 95% or more. On the other hand, powdered activated carbon refers to activated carbon with a particle size of less than 0.150 mm as specified in JIS K1474. Furthermore, fibrous activated carbon refers to activated carbon having a fibrous shape.

[0077] The average particle diameter of the adsorbent of the present invention is not particularly limited and activated carbon of each particle size can be used, but from the perspective of operability before and after the reaction or reaction efficiency, it can preferably be 0.1 μm to 10,000 μm, more preferably 1 μm to 3,000 μm.

[0078] Since the ignition residue contained in the activated carbon used in the carrier of the present invention may cause unexpected side reactions in the catalytic reaction, it is preferably 10% or less, more preferably 1% or less.

[0079] The method for reactivating activated carbon according to the present invention is not particularly limited. For example, it can be obtained by a manufacturing method comprising a process of steam reactivation treatment or chemical reactivation treatment using an activated carbon precursor.

[0080] The raw material of the activated carbon used in the carrier of the present invention is not particularly limited as long as it is a commonly used carbon source, but examples include wood, wood powder, coconut shells, coal, carbonized phenolic resin, etc. Among these, plant raw materials are preferred from the perspective of having a low impurity content, and wood powder, coconut shells, etc. are more preferred.

[0081] There are no particular restrictions on the process after revival, and any activated carbon manufactured through the known cleaning process, heat treatment process, and crushing and classification process required to satisfy the above characteristics may be used.

[0082] [Ruthenium complex]

[0083] The ruthenium complex represented by general formulas (1-1) and (1-2) contained in the catalyst of the present invention will be described in detail. The ruthenium complex represented by general formulas (1-1) and (1-2) used in the present invention is characterized by having a diamine ligand, an aromatic compound (arene) ligand, and an anionic group.

[0084] In the general formulas (1-1) and (1-2) used in the present invention, solid lines represent single bonds, double lines represent double bonds, and dashed lines represent coordinate bonds; Ru represents a ruthenium atom, N represents a nitrogen atom, S represents a sulfur atom, and O represents an oxygen atom. The * mark in general formulas (1-1) and (1-2) indicates that the carbon atom to which the * mark is attached may be a non-carbon atom. When the carbon atom is a non-carbon atom, it may be an optically active material, a mixture of optically active materials, or a racemic mixture (including racemic compounds). As a preferred embodiment of the present invention, when the carbon atom is a non-carbon atom, the optically active materials may be used.

[0085] [Chemical Formula 3]

[0086]

[0087] In general formula (1-1), j and k are integers of 0 or 1, and j+k is not 1. General formula (1-1) represents the case where j and k are 1, and general formula (1-2) represents the case where j and k in general formula (1-1) are 0. When j and k are 1, the bond between the ruthenium atom and the nitrogen atom is a coordinate bond, indicated by a dashed line, and when j and k are 0, the bond between the ruthenium atom and the nitrogen atom is a covalent bond, indicated by a solid line.

[0088] In general formula (1-1), X represents an anionic group and Y represents a hydrogen atom.

[0089] Examples of anionic groups represented by X in general formula (1-1) include trifluoromethanesulfonyloxy groups, p-toluenesulfonyloxy groups, methanesulfonyloxy groups, benzenesulfonyloxy groups, hydrogen atoms, or halogen atoms. Preferred X includes hydrogen atoms and halogen atoms, specifically fluorine atoms, chlorine atoms and bromine atoms, and for example, chlorine atoms are particularly preferred.

[0090] As for the hydrogen atom at position Y of general formula (1-1) and the hydrogen atom at position X of general formula (1-1) (i.e., the hydrogen atom bonded to Ru in general formula (1-2)), they may be ordinary hydrogen atoms as well as isotopes of hydrogen atoms. A preferred isotope is a deuterium atom.

[0091] <Sulfonyl site (R 1 )>

[0092] R of general formulas (1-1) and (1-2) 1 It represents an alkyl group; a 10-camparyl group; an aryl group that may have a substituent; or an aralkyl group that may have a substituent.

[0093] ≪Sulfonyl site (R 1 ): Alkyl group≫

[0094] R of general formulas (1-1) and (1-2) 1 As an alkyl group represented by, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, may be used. Specific alkyl groups include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0095] Also, R of general formulas (1-1) and (1-2) 1The alkyl group represented by may have one or more substituents selected from halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms. Examples include perfluoroalkyl groups such as trifluoromethyl groups, pentafluoroethyl groups, and heptafluoropropyl groups.

[0096] ≪Sulfonyl site (R 1 ): Aryl group that may have substituents≫

[0097] R of general formulas (1-1) and (1-2) 1 Examples of aryl groups represented by 6 to 30 carbon atoms include aromatic monocyclic, aromatic polycyclic, or aromatic condensed-ring groups, preferably aromatic monocyclic, aromatic polycyclic, or aromatic condensed-ring groups having 6 to 15 carbon atoms, and particularly preferably aromatic monocyclic groups having 6 to 12 carbon atoms. Specific examples of aryl groups having 6 to 30 carbon atoms include phenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, indenyl groups, etc., preferably phenyl groups.

[0098] Also, R of general formulas (1-1) and (1-2) 1 The aryl group represented by is an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 10 carbon atoms, a halogen atom, a cyano group (-CN), an amino group, or an alkylamino group (-NR 11 R 12 ), 5- or 6-membered cyclic amino group, acylamino group (-NH-CO-R 11 ), hydroxyl group, alkoxy group (-OR 11 ), acyl(-CO)-R 11 ), carboxyl group, alkoxycarbonyl group (-COOR 11 ), phenoxycarbonyl group, and alkylthio group (-SR 11 It may have one or more substituents selected from ).

[0099] The alkyl group in question as a substituent is R of the general formulas (1-1) and (1-2) described above. 1The alkyl group can be selected from the defined group represented by, preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms. In addition, the alkyl group as a substituent may have one or more substituents selected from halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms.

[0100] -NR 11 R 12 An alkylamino group represented by (where R 11 , R 12 Each of the groups independently represents a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; or a cycloalkyl group having 3 to 10 carbon atoms. Examples of monoalkylamino groups or dialkylamino groups such as N-methylamino groups, N,N-dimethylamino groups, N,N-diisopropylamino groups, or N-cyclohexylamino groups may be included. Examples of cyclic amino groups having 1 or 2 nitrogen atoms in 5 to 6 groups may be unsaturated or saturated heterocyclic groups having 1 or 2 nitrogen atoms, such as pyrrolidinyl groups, piperidino groups, or morphonyl groups.

[0101] -CO-R 11 Asilgi represented by (here R 11 Examples of groups that represent hydrogen atoms; alkyl groups having 1 to 10 carbon atoms; or cycloalkyl groups having 3 to 10 carbon atoms include formyl groups, acetyl groups, propionyl groups, butyryl groups, pivaloyl groups, pentanoyyl groups, or hexanoyl groups.

[0102] -NH-CO-R 11 An acylamino group represented by (where, R 11 Examples of groups that represent hydrogen atoms; alkyl groups having 1 to 10 carbon atoms; or cycloalkyl groups having 3 to 10 carbon atoms include formylamino groups, acetylamino groups, propionylamino groups, pivaloylamino groups, pentanoyamino groups, or hexanoylamino groups.

[0103] -OR 11 an alkoxy group represented by (here, R11 (Examples include a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; or a cycloalkyl group having 3 to 10 carbon atoms.) Examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group, a 2-methylbutoxy group, a 3-methylbutoxy group, a 2,2-dimethylpropyloxy group, an n-hexyloxy group, a 2-methylpentyloxy group, a 3-methylpentyloxy group, a 4-methylpentyloxy group, a 5-methylpentyloxy group, or a cyclohexyloxy group.

[0104] -COO-R 11 an alkoxycarbonyl group represented by (where, R 11 (As a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; or a cycloalkyl group having 3 to 10 carbon atoms, examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, or a 2-ethylhexyloxycarbonyl group.)

[0105] -SR 11 An alkylthio group represented by (where, R 11 (Examples include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms; or a cycloalkyl group having 3 to 10 carbon atoms.) Examples include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an s-butylthio group, an isobutylthio group, a t-butylthio group, a pentylthio group, a hexylthio group, or a cyclohexyl group.

[0106] R of general formulas (1-1) and (1-2) 1Specific examples of aryl groups that may have a substituent represented by, such as, phenyl group, o-, m- and p-tolyl group, o-, m- and p-ethylphenyl group, o-, m- and p-isopropylphenyl group, o-, m- and pt-butylphenyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group, 4-trifluoromethylphenyl group, 2,4,6-trichlorophenyl group, pentafluorophenyl group, etc.

[0107] ≪Sulfonyl site (R 1 ): Aralkyl group (may have a substituent)≫

[0108] R of general formulas (1-1) and (1-2) 1 Examples of aralkyl groups represented by include benzyl groups, phenethyl groups, etc.

[0109] Also, R of general formulas (1-1) and (1-2) 1 The aralkyl group represented by may have an alkyl group having 1 to 10 carbon atoms as a substituent.

[0110] R of general formulas (1-1) and (1-2) 1 Examples of aralkyl groups substituted with specific substituents represented by include o-, m- and p-methylbenzyl groups, 2,6-dimethylbenzyl groups, 2,4,6-trimethylbenzyl groups, 2,4,6-triisopropylbenzyl groups, etc.

[0111] <Diamine site (R 2 , R 3 )>

[0112] R of general formulas (1-1) and (1-2) 2 and R 3 Each independently represents a hydrogen atom; or a phenyl group, or R 2 and R 3 They combine with each other to form R 2 and R 3 It forms a cycloalkane ring of 4 to 8 members together with the bonded carbon atoms.

[0113] ≪Diamine site (R 2 , R 3 ): phenyl group≫

[0114] R of general formulas (1-1) and (1-2) 2 and R 3 The phenyl group represented by may have one or more substituents selected from alkyl groups, halogen atoms, and alkoxy groups.

[0115] The alkyl group as a substituent is R of the general formulas (1-1) and (1-2) described above. 2 and R 3 It may be selected from groups defined as alkyl groups represented by, but preferably, straight-chain or branched-chain alkyl groups having 1 to 5 carbon atoms may be included.

[0116] Examples of the halogen atoms serving as substituents include fluorine atoms or chlorine atoms.

[0117] The alkoxy group as a substituent may be a straight-chain or branched-chain alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Specific alkoxy groups may include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, and an n-decyloxy group.

[0118] ≪Diamine site (R 2 , R 3 ): R 2 and R 3 This ring formation≫

[0119] R of general formulas (1-1) and (1-2) 2 and R 3 In the case where they are combined with each other, R 2 and R 3Together with the carbon atoms to which they are bonded, they form a straight-chain or branched-chain alkylene group having 2 to 10 carbon atoms, preferably 3 to 10, and together with adjacent carbon atoms, they form a cycloalkane ring having 4 to 8 members, preferably 5 to 8 members. These rings may have alkyl groups such as methyl groups, isopropyl groups, and t-butyl groups as substituents.

[0120] < Amine phase substituent (R 4 )>

[0121] R in general formulas (1-1) and (1-2) 4 is a hydrogen atom; or, represents an alkyl group that may have a substituent, or R 5 It may be combined with to form two cross-linked sites as shown in formula (W). When said cross-linked sites are formed, the ruthenium complex becomes a tethered type.

[0122] [Chemical Formula 4]

[0123]

[0124] In equation (W), n 1 The dashed line portion of the carbon chain end containing R in formulas (1-1) and (1-2) 5 Instead, it bonds to the carbon atom of the arene site, and n in formula (W) 2 The dashed line portion of the carbon chain end containing R in formulas (1-1) and (1-2) 4 Instead, it bonds to the nitrogen atom of the amine site. Z represents a methylene group, an oxygen atom, or a sulfur atom. n 1 is 1 or 2, n 2 is any integer from 1 to 3.

[0125] ≪ Amine phase substituent (R 4 ): Alkyl group≫

[0126] R of general formulas (1-1) and (1-2) 4As an alkyl group represented by, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, may be used. Specific alkyl groups include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0127] Also, R of general formulas (1-1) and (1-2) 4 The alkyl group represented by may have one or more substituents selected from halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms. Examples include perfluoroalkyl groups such as trifluoromethyl groups, pentafluoroethyl groups, and heptafluoropropyl groups.

[0128] ≪ Amine phase substituent (R 4 ): When the bridge site is formed≫

[0129] R of general formulas (1-1) and (1-2) 4 is R 5 When combined with to form a cross-linking site of the divalent group represented by formula (W), Z in the general formula (W) represents a methylene group or an oxygen atom. Preferred Z may be an oxygen atom.

[0130] n in the general formula (W) 1 represents an integer of 1 or 2, and the preferred n 1 As for , 1 can be cited. n 2 represents an integer from 1 to 3, and the preferred n 2 As for that, 2 can be cited.

[0131] <Aren part (R 5 -R 10 )>

[0132] R of the aren region represented by general formulas (1-1) and (1-2). 5 , R 6 , R 7 , R8 , R 9 , R 10 Each represents independently a hydrogen atom; an alkyl group; a hydroxyl group; or an alkoxy group. Or R 5 is R 4 And it is possible to form a cross-linked region as shown in the above formula (W).

[0133] ≪Aren part (R 5 -R 10 ): Alkyl group≫

[0134] R of general formulas (1-1) and (1-2) 5 , R 6 , R 7 , R 8 , R 9 , R 10 As an alkyl group represented by, examples include straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Specific examples of alkyl groups include, for instance, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, s-butyl groups, t-butyl groups, n-pentyl groups, n-hexyl groups, n-heptyl groups, n-octyl groups, n-nonyl groups, and n-decyl groups.

[0135] ≪Aren part (R 5 -R 10 ): Alkoxygenation≫

[0136] R of general formulas (1-1) and (1-2) 5 , R 6 , R 7 , R 8 , R 9 , R 10The alkoxy group represented by [the symbol] may be a straight-chain or branched-chain alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Specific alkoxy groups may include, for example, methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, s-butoxy groups, isobutoxy groups, t-butoxy groups, n-pentyloxy groups, n-hexyloxy groups, n-heptyloxy groups, n-octyloxy groups, n-nonyloxy groups, and n-decyloxy groups.

[0137] R in general formulas (1-1) and (1-2) 4 and R 5 In the case where the complex does not form the cross-linking site shown in formula (W) (i.e., a non-tethered ruthenium complex), R 4 is preferably a hydrogen atom, and / or, R 1 It is preferable that this is a 4-methylphenyl group, a 2,3,4,5,6-pentafluorophenyl group, a methyl group, an isobutyl group, a benzyl group, a 2',5'-dimethylbenzyl group, or a 10-camparyl group, and / or R 2 and R 3 It is preferable that the phenyl groups or bond with each other to form a cyclohexane ring, and / or R 5 , R 6 , R 7 , R 8 , R 9 , R 10 It is preferable that the silver be a hydrogen atom, a methyl group, or an isopropyl group.

[0138] R in general formulas (1-1) and (1-2) 4 and R 5 Specific examples of complexes that do not form the crosslinking sites shown in formula (W) (i.e., non-tethered ruthenium complexes) include, for instance, the following compounds, but are not limited thereto.

[0139] Additionally, the compound name and the abbreviation (in parentheses) in this specification are listed together below.

[0140] Chloro(benzene[(R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0141] (RuCl((R,R)-Ts-DPEN)(Benzene))

[0142] Chloro(benzene[(S,S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0143] (RuCl((S,S)-Ts-DPEN)(Benzene))

[0144] Chloro(meshtylene)[(R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0145] (RuCl((R,R)-Ts-DPEN)(Mesitylene))

[0146] Chloro(meshtylene)[(S,S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0147] (RuCl((S,S)-Ts-DPEN)(Mesitylene))

[0148] Chloro(meshtylene)[(R,R)-N-(methanesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0149] (RuCl((R,R)-Ms-DPEN)(Mesitylene))

[0150] Chloro(meshtylene)[(S,S)-N-(methanesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0151] (RuCl((S,S)-Ms-DPEN)(Mesitylene))

[0152] Chloro(meshtylene)[(R,R)-N-(benzylsulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0153] (RuCl((R,R)-BnSO2-DPEN)(Mesitylene))

[0154] Chloro(meshtylene)[(S,S)-N-(benzylsulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0155] (RuCl((S,S)-BnSO2-DPEN)(Mesitylene))

[0156] Chloro(meshtylene)[(R,R)-N-(isobutansulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0157] (RuCl((R,R)-i-BuSO2-DPEN)(Mesitylene))

[0158] Chloro(meshtylene)[(S,S)-N-(isobutansulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0159] (RuCl((S,S)-i-BuSO2-DPEN)(Mesitylene))

[0160] Chloro(meshtylene)[(R,R)-N-(2', 6'-dimethylbenzylsulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0161] (RuCl((R,R)-2',6'-(CH3)2BnSO2-DPEN)(Mesitylene))

[0162] Chloro(meshtylene)[(S,S)-N-(2', 6'-dimethylbenzylsulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0163] (RuCl((S,S)-2',6'-(CH3)2BnSO2-DPEN)(Mesitylene))

[0164] Chloro(p-cymene)[(R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0165] (RuCl((R,R)-Ts-DPEN)(p-cymen))

[0166] Chloro(p-cymene)[(S,S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0167] (RuCl((S,S)-Ts-DPEN)(p-cymen))

[0168] (p-cymene)[(R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II) triplate

[0169] (Ru(OTf)((R,R)-Ts-DPEN)(p-Symen))

[0170] (p-cymene)[(S,S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II) triplate

[0171] (Ru(OTf)((S,S)-Ts-DPEN)(p-Symen))

[0172] (p-cymene)[(R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)hydride

[0173] (RuH((R,R)-Ts-DPEN)(p-Symen))

[0174] (p-cymene)[(S,S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)hydride

[0175] (RuH((S,S)-Ts-DPEN)(p-Symen))

[0176] (p-cymene)[(R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0177] (Ru((R,R)-Ts-DPEN)(p-Symen))

[0178] (p-cymene)[(S,S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0179] (Ru((S,S)-Ts-DPEN)(p-Symen))

[0180] Chloro(p-cymene)[(R,R)-N-(methanesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0181] (RuCl((R,R)-Ms-DPEN)(p-cymen))

[0182] Chloro(p-cymene)[(S,S)-N-(methanesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0183] (RuCl((S,S)-Ms-DPEN)(p-cymen))

[0184] Chloro(p-cymene)[(R,R)-N-(pentafluorobenzenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0185] (RuCl((R,R)-Fs-DPEN)(p-cymen))

[0186] Chloro(p-cymene)[(S,S)-N-(pentafluorobenzenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0187] (RuCl((S,S)-Fs-DPEN)(p-cymen))

[0188] Chloro(p-cymene)[(R,R)-N-(benzylsulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0189] (RuCl((R,R)-BnSO2-DPEN)(p-cymene))

[0190] Chloro(p-cymene)[(S,S)-N-(benzylsulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0191] (RuCl((S,S)-BnSO2-DPEN)(p-cymene))

[0192] Chloro((p-cymene)[(R,R)-N-(isobutansulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0193] (RuCl((R,R)-i-BuSO2-DPEN)(p-cymen))

[0194] Chloro(p-cymene)[(S,S)-N-(isobutansulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0195] (RuCl((S,S)-i-BuSO2-DPEN)(p-cymen))

[0196] Chloro(p-cymene)[(R,R)-N-(2', 6'-dimethylbenzylsulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0197] (RuCl((R,R)-2',6'-(CH3)2BnSO2-DPEN)(p-cymen))

[0198] Chloro(p-cymene)[(S,S)-N-(2', 6'-dimethylbenzylsulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0199] (RuCl((S,S)-2',6'-(CH3)2BnSO2-DPEN)(p-cymen))

[0200] Chloro(p-cymene)[(R,R)-N-((1R)-camphor-sulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0201] (RuCl((R)-Cs-(R,R)-DPEN)(p-cymen))

[0202] Chloro(p-cymene)[(S,S)-N-((1S)-camphor-sulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)

[0203] (RuCl((S)-Cs-(S,S)-DPEN)(p-cymen))

[0204] Chloro(p-cymene)[(R,R)-N-(p-toluenesulfonyl)-1,2-cyclohexanediamine]ruthenium(II)

[0205] (RuCl((R,R)-Ts-DACH)(p-cymen))

[0206] Chloro(p-cymene)[(S,S)-N-(p-toluenesulfonyl)-1,2-cyclohexanediamine]ruthenium(II)

[0207] (RuCl((S,S)-Ts-DACH)(p-cymene))

[0208] R in general formulas (1-1) and (1-2) 4 and R 5 In the case where the complex forms the cross-linking site represented by formula (W) (i.e., a tether-type ruthenium complex), it is preferable that Z is an oxygen atom, and / or, n 1 It is desirable that this is 1, and / or, n 2 It is preferable that is 2, and / or, R 1 It is preferable that this is a 4-methylphenyl group or a methyl group, and / or, R 2 and R 3 It is preferable that this is a phenyl group, and / or, R 6 , R 7 , R 9 , R 10 It is preferable that this be a hydrogen atom, and / or, R 8 It is preferable that this be a methyl group.

[0209] R in general formulas (1-1) and (1-2) 4 and R 5 Specific examples of the complex forming the crosslinking site shown in formula (W) (i.e., a tether-type ruthenium complex) include, for instance, the following compounds, but are not limited thereto. Additionally, the names of the compounds and their abbreviations (in parentheses) in this specification are listed together below.

[0210] Chloro[(R,R)-N-[2-[2-(4-methylbenzyloxy)ethyl]amino-1,2-diphenylethyl]-p-toluenesulfonamide]ruthenium(II)

[0211] ((R,R)-Ts-DENEB(Registered Trademark))

[0212] Chloro[(S,S)-N-[2-[2-(4-methylbenzyloxy)ethyl]amino-1,2-diphenylethyl]-p-toluenesulfonamide]ruthenium(II)

[0213] ((S,S)-Ts-DENEB(Registered Trademark))

[0214] Chloro[(R,R)-N-[2-[2-(4-methylbenzyloxy)ethyl]amino-1,2-diphenylethyl]-methanesulfonamide]ruthenium(II)

[0215] ((R,R)-Ms-DENEB(Registered Trademark))

[0216] Chloro[(S,S)-N-[2-[2-(4-methylbenzyloxy)ethyl]amino-1,2-diphenylethyl]-methanesulfonamide]ruthenium(II)

[0217] ((S,S)-Ms-DENEB(Registered Trademark))

[0218] Chloro[(R,R)-N-[2-(3-phenylpropyl)amino-1,2-diphenylethyl]-p-toluenesulfonamide]ruthenium(II)

[0219] (RuCl(benz-C3-teth-(R,R)-Ts-DPEN))

[0220] Chloro[(S,S)-N-[2-(3-phenylpropyl)amino-1,2-diphenylethyl]-p-toluenesulfonamide]ruthenium(II)

[0221] (RuCl(benz-C3-teth-(S,S)-Ts-DPEN))

[0222] Chloro[(R,R)-N-[2-(3-phenylpropyl)amino-1,2-diphenylethyl]-methanesulfonamide]ruthenium(II)

[0223] (RuCl(benz-C3-teth-(R,R)-Ms-DPEN))

[0224] Chloro[(S,S)-N-[2-(3-phenylpropyl)amino-1,2-diphenylethyl]-methanesulfonamide]ruthenium(II)

[0225] (RuCl(benz-C3-teth-(S,S)-Ms-DPEN))

[0226] The ruthenium complex, which is a constituent element of the catalyst according to the present invention, can be synthesized by a person skilled in the art, for example, by the method described in Patent Publication No. 3040353 or Patent Publication No. 5718178. In addition, the ruthenium complex may be commercially available.

[0227] <Method for preparing catalyst: Regarding the state of the complex or the preparation solvent>

[0228] The catalyst of the present invention is obtained by reacting a ruthenium complex of general formula (1-1) and / or (1-2) with activated carbon in a solvent.

[0229] When preparing, the state of the complex is not particularly limited, but it is preferable to dissolve it in the preparation solvent. In this case, the solvent used is not particularly limited, but protonic polar solvents such as methanol, ethanol, and water are preferred, and methanol is particularly preferred. In addition, if the complex is difficult to dissolve in the preparation solvent, two or more types of solvents may be mixed and used as needed.

[0230] In addition, regarding the catalyst of the present invention, although not particularly limited, as described above, it is preferable to prepare it such that the total mass of the ruthenium complex is typically in the range of 0.1 mass% to 25 mass% with respect to the total mass of the activated carbon.

[0231] ≪Impregulation Conditions: Regarding Heating and Stirring Conditions≫

[0232] During the reaction, stirring or letting the mixture stand may be performed. Heating may or may not be performed during preparation. While the reaction solution immediately after the start of preparation generally exhibits a dark brown color, discoloration of the reaction solution as impregnation proceeds is observed over time. The preparation completion time varies depending on the type and loading amount of activated carbon and complex, but for practical purposes, various conditions should be set so that impregnation is completed within 12 hours to 7 days. The solvent after preparation may be removed by evaporation or by filtration.

[0233] ≪Immersion Conditions: Regarding Washing and Drying Conditions≫

[0234] The activated carbon powder obtained after removing the manufacturing solvent is washed with an organic solvent. The washing solvent is not particularly limited, but it is preferable to use the same solvent used during preparation.

[0235] The obtained activated carbon-supported complex may or may not contain a cleaning solvent, but it is preferable to remove it by vacuum drying. The vacuum level during vacuum drying is not particularly limited, but it is generally preferable to be 20 torr or less. Heating may be performed as necessary, and the heating temperature is preferably 40℃ or less.

[0236] Catalytic reaction

[0237] A reduction product can be produced by using the catalyst of the present invention described above and reducing an organic compound in the presence of a hydrogen donor.

[0238] The reduction reaction of the present invention includes a method for producing an alcohol by reducing the carbonyl group of a carbonyl compound, such as a ketone, in the presence of a hydrogen donor and using a catalyst according to the present invention, and / or a method for producing an amine by reducing the imino group of an imine compound. In addition, when the above-described activated carbon-supported ruthenium complex is an optically active material, an optically active alcohol can be produced by reducing the carbonyl group of a carbonyl compound without an agent, and an optically active amine can be produced by reducing the imino group of an imine compound.

[0239] As a hydrogen donor, any substance commonly used in hydrogen transfer type reduction reactions, such as formic acid or its alkali metal salt, or isopropanol, an alcohol having a hydrogen atom at the α-position of the carbon atom substituted by a hydroxyl group, is not particularly limited. Additionally, hydrogen gas may also be used as a hydrogen donor.

[0240] The solvent used in the reaction can be a liquid hydrogen donor, but it is also possible to use non-hydrogen donating solvents such as toluene, tetrahydrofuran, acetonitrile, dimethylformamide, dimethyl sulfoxide, acetone, and methylene chloride, or water, methanol, ethanol, and n-butanol, either alone or in combination.

[0241] ≪When using formate≫

[0242] When carrying out a reduction reaction, if a formate is used as a hydrogen donor, it is preferable to use water together with an organic solvent to dissolve the hydrogen donor. The organic solvent used is not particularly limited, but a solvent that is easily miscible with water is preferred, and examples include methanol, ethanol, and n-butanol.

[0243] ≪When using formic acid≫

[0244] When carrying out a reduction reaction, if formic acid is used as the hydrogen donor, it is preferable to carry out the reaction in the presence of a base such as a tertiary organic amine or an inorganic base, and it is more preferable to carry out the reaction in the presence of a tertiary organic amine. The amine used is not particularly limited, but examples include tertiary organic amines such as trimethylamine, triethylamine, triisopropylamine, 1,4-diazabicyclo[2,2,2]octane (DABCO), and 1,8-diazabicyclo[5,4,0]undeca-7-ene (DBU).

[0245] In this case, formic acid and amine may be added to the reaction system separately or mixed and added to the reaction system. When used in combination, formic acid and amine may be mixed in any ratio. Additionally, an azeotropic mixture of formic acid and amine may be prepared in advance and used. Preferred azeotropic mixtures of formic acid and amine include, for example, a triethylamine formic acid (5:2 (molar ratio)) azeotropic mixture.

[0246] When the catalyst according to the present invention is used as a reduction catalyst, the amount used is preferably selected from the range of 10 to 1,000,000, preferably 50 to 15,000, where the molar ratio (S / C) of the substrate (carbonyl compound or imine) (S) to the ruthenium metal atom (C) is 10 to 1,000,000.

[0247] ≪Amount of hydrogen donor≫

[0248] The amount of hydrogen donor to the carbonyl compound is typically used in an equimolar amount or more. Among these, if the hydrogen donor is formic acid or its salt, it is preferably used in an amount of 1.5 times the molar amount or more, and in a range of 40 times the molar amount or less, preferably 20 times the molar amount or less. From the perspective of molecular efficiency, it is preferable to use an amount of 2 to 20 times the molar amount. On the other hand, if the hydrogen donor is isopropanol, etc., it is used in a large excess relative to the substrate from the perspective of reaction equilibrium, and is typically used in a range of 100 times the molar amount or less.

[0249] ≪Details of Reaction Conditions≫

[0250] The reaction temperature is selected from the range of -20 to 100°C, preferably 0 to 70°C.

[0251] The reaction pressure is not particularly limited and is typically carried out at 0.5 to 2 atmospheres, preferably at atmospheric pressure. In addition, when hydrogen gas is used, it is typically 5 MPa or less.

[0252] The reaction time varies depending on the catalyst ratio to the substrate, but is carried out in the range of 1 to 100 hours, usually 2 to 50 hours.

[0253] ≪Regarding Reuse≫

[0254] After the reaction is completed, the reaction solution of the catalyst according to the present invention and the reduced target product can be separated by simple methods such as decanting or filtration. In addition, the catalyst of the present invention separated by decanting, etc., can be reused as is for the next reaction. From the reaction solution after removing the catalyst, the generated product or optically active material can be separated and purified by general operations such as distillation, extraction, chromatography, and recrystallization.

[0255] ≪On Flow Reactions≫

[0256] Furthermore, in the reduction reaction of the present invention, a continuous flow reaction can be performed by utilizing the characteristics of the activated carbon-supported ruthenium complex. That is, after packing the activated carbon-supported ruthenium complex into a column, the column is maintained at the reaction temperature described above, and the substrate, hydrogen donor, and solvent are supplied by a quantitative pump; thereby, an organic compound can be reduced to produce a reduced product without the need for catalyst separation operations. The reaction conditions are the same as described above.

[0257] The reaction can be carried out, for example, by preparing a mixture of a substrate, a solvent, a base, and a hydrogen donor, and transferring it to a column using an HPLC pump. Additionally, if the hydrogen donor is hydrogen gas, the reaction can be carried out by mixing the substrate, solvent, and base, transferring the mixture to the column, and simultaneously passing hydrogen gas through the column.

[0258] Examples

[0259] Hereinafter, catalytic reactions using the compounds and catalysts of the present invention will be described in detail with reference to examples, but the present invention is not limited in any way by these examples. Among the examples, the apparatus and conditions used for measuring physical properties are as follows.

[0260] 1) Gas Chromatography (GC): GC-4000Plus type instrument (GL Sciences Inc.)

[0261] [Measurement Condition 1] Column: CP-Chirasil-DEX CB (Agilent), Sample Inlet: 250℃, Sample Detector: 250℃, Measurement Temperature: 120℃, Holding Time: 15 min.

[0262] [Measurement Condition 2] Column: CP-Chirasil-DEX CB (Agilent), Sample Inlet: 250℃, Sample Detector: 250℃, Measurement Temperature: 120℃, Holding Time: 30 min.

[0263] [Measurement Condition 3] Column: CP-Chirasil-DEX CB (Agilent), Sample Inlet: 250℃, Sample Detector: 250℃, Measurement Temperature: 150℃, Holding Time: 25 min.

[0264] [Measurement Condition 4] Column: CP-Chirasil-DEX CB (Agilent), Sample Inlet: 250℃, Sample Detector: 250℃, Measurement Temperature: 120℃, Holding Time: 35 min.

[0265] [Measurement Condition 5] Column: CP-Chirasil-DEX CB (Agilent), Sample Inlet: 250℃, Sample Detector: 250℃, Measurement Temperature: 60℃, Holding Time: 30 min.

[0266] 2) Plasma (ICP) Emission Spectroscopic Analyzer

[0267] ICP emission spectroscopy was used to analyze the amount of leached metal. Among the examples, the apparatus and conditions used to analyze the amount of leached ruthenium are as follows.

[0268] Device: Optima8300(Perkin Elmer)

[0269] High-frequency output: 1.5 kW

[0270] Plasma gas flow rate: 12 mL / min (argon gas)

[0271] Auxiliary gas flow rate: 0.4 L / min (argon gas)

[0272] Carrier gas flow rate: 0.35 L / min (argon gas)

[0273] Sample introduction rate: 0.8 mL / min

[0274] Chamber: Cyclone Chamber

[0275] 3) Proton nuclear magnetic resonance spectroscopy ( 1 ¹H NMR): 400-MR DD2 type device (Resonance frequency: 400 MHz) (Agilent)

[0276] 4) SEM-EDS

[0277] SEM-EDS was used for the analysis of ruthenium on the catalyst.

[0278] Analysis device: TM-3000 (Hitachi High-Tech Science Corporation)

[0279] Analysis software: SwiftED Ver. 1.7 (Oxford Instruments)

[0280] Acceleration voltage: 15 kV

[0281] The characteristic X-ray energies of the elements to be analyzed are as shown in Table 1.

[0282] element Characteristic X-ray energy (kV) element Characteristic X-ray energy (kV) element Characteristic X-ray energy (kV) C 0.28 Cl 2.62 Zn 8.64 N 0.39 2.82 9.57 O 0.53 0.18 1.01 Na 1.04 K 3.31 0.71 Mg 1.25 3.59 0.88 Al 1.49 0.26 Ru 19.28 Si 1.74 Ca 3.69 2.56 P 2.01 4.01 2.68 2.14 0.34 2.38 S 2.31 0.31 3.18 2.46 2.25

[0283] The activated carbon used in this embodiment is as shown in Table 2.

[0284] Ignition residue (%) Specific surface area (m²) 2 / g) Average pore diameter (nm) Average particle diameter (μm) Surface functional groups (mmol / g) A1 － 1583 1.84 － － A2 0.2 1610 1.84 44.7 0.15 B1 － 927 1.82 － － B2 － 994 1.81 － － C1 － 1455 3.57 － － M － 899 2.23 － － C2 0.3 1467 3.84 57.1 0.23 A1 prize － 1685 1.85 － － A2 prize 0.1 1739 1.86 324 0.16 B1 prize － 1044 1.77 － － B2 prize － 1037 1.76 － － C2 prize 0.6 1487 3.29 380 0.22

[0285] In addition, "DENEB" described in the examples is a registered trademark of Takasago Flavoring Industry Co., Ltd., as described above.

[0286] [Example 1] Preparation of a catalyst (catalyst 1) containing chloro[(R,R)-N-[2-[2-(4-methylbenzyloxy)ethyl]amino-1,2-diphenylethyl]-p-toluenesulfonamide]ruthenium(II) adsorbed on powdered activated carbon (A1)

[0287] A complex solution was prepared by adding chloro[(R,R)-N-[2-[2-(4-methylbenzyloxy)ethyl]amino-1,2-diphenylethyl]-p-toluenesulfonamide]ruthenium(II) ((R,R)-Ts-DENEB (manufactured by Takasago Fragrance Industry Co., Ltd.), 40.7 mg, 0.0626 mmol), dehydrated toluene (39 mL), and dehydrated ethanol (2 mL) to a 200 mL beaker and dissolving them completely. After adding activated carbon (A1, 5.00 g) to a 300 mL beaker, the complex solution was added over a period of 1 minute. The resulting suspension was left to stand until the solvent was removed by distillation. Dehydrated toluene (30 mL) and dehydrated ethanol (1.5 mL) were added to the resulting solid component, stirred for 1 minute, and then filtered. After transferring the obtained solid to a 300 mL beaker, dehydrated toluene (30 mL) and dehydrated ethanol (1.5 mL) were added and stirred for 1 minute, after which it was filtered. The solid component recovered by filtration was vacuum dried at 40°C for 24 hours to obtain 6.56 g of Compound 1. The filtrate was concentrated under reduced pressure, and the amount of ruthenium contained in the recovered residue was measured by ICP analysis. As a result, it was found that the unadsorbed ruthenium component was 0.3% relative to the used ruthenium component, so the adsorption rate of the complex was 99.7%, and the amount loaded as a complex on the activated carbon was 0.81 mass%.

[0288] [Example 2] Preparation of a catalyst (catalyst 2) comprising a (R,R)-Ts-DENEB complex adsorbed on powdered activated carbon (A2)

[0289] Compound 2 was obtained in an amount of 6.62 g by the same method as in Example 1, except that A2 (5.00 g) was used for the activated carbon. The filtrate was concentrated under reduced pressure, and the amount of ruthenium contained in the recovered trace residue was measured by ICP analysis. As a result, the unadsorbed ruthenium component was 0.7%, so it was found that the adsorption rate of the complex was 99.3% and the amount of the complex loaded on the activated carbon was 0.80 mass%.

[0290] [Example 3] Preparation of a catalyst (catalyst 3) comprising a (R,R)-Ts-DENEB complex adsorbed on powdered activated carbon (B1)

[0291] 6.10 g of compound 3 was obtained by the same method as in Example 1, except that B1 (5.00 g) was used on the activated carbon. When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 8.9 mg, so the adsorption rate of the complex was 78.1%, and the amount of complex loaded on the activated carbon was 0.63 mass%.

[0292] [Example 4] Preparation of a catalyst (catalyst 4) comprising a (R,R)-Ts-DENEB complex adsorbed on powdered activated carbon (B2)

[0293] 6.17 g of compound 4 was obtained by the same method as in Example 1, except that B2 (5.00 g) was used for the activated carbon. When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 9.0 mg, so the adsorption rate of the complex was 77.9%, and the amount of complex loaded onto the activated carbon was 0.63 mass%.

[0294] [Example 5] Preparation of a catalyst (catalyst 5) comprising a (R,R)-Ts-DENEB complex adsorbed on powdered activated carbon (C1)

[0295] 5.74 g of compound 5 was obtained by the same method as in Example 1, except that C1 (5.00 g) was used for the activated carbon. The filtrate was concentrated under reduced pressure, but no solid components were recovered. That is, the adsorption rate of the complex was 100%, and the amount of complex loaded onto the activated carbon was 0.81 mass%.

[0296] [Example 6] Preparation of a catalyst (catalyst 6) comprising a (R,R)-Ts-DENEB complex adsorbed on powdered activated carbon (C2)

[0297] 5.85 g of compound 6 was obtained by the same method as in Example 1, except that C2 (5.00 g) was used for the activated carbon. The filtrate was concentrated under reduced pressure, and the amount of ruthenium contained in the recovered trace residue was measured by ICP analysis. As a result, the unadsorbed ruthenium component was 1.0%, so it was found that the adsorption rate of the complex was 99.0% and the loading amount as a complex on the activated carbon was 0.80 mass%.

[0298] [Example 7] Preparation of a catalyst (catalyst 7) ​​comprising a (R,R)-Ts-DENEB complex adsorbed on powdered activated carbon (M)

[0299] 5.82 g of compound 7 was obtained by the same method as in Example 1, except that M (5.00 g) was used for the activated carbon. The filtrate was concentrated under reduced pressure, but no solid components were recovered. That is, the adsorption rate of the complex was 100%, and the amount of complex loaded onto the activated carbon was 0.81 mass%.

[0300] [Example 8] Preparation of a catalyst (catalyst 8) containing a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (A1, granular). 6.02 g of compound 8 was obtained by the same method as in Example 1, except that A1 (granular, 5.00 g) was used for the activated carbon. The filtrate was concentrated under reduced pressure, but no solid components were recovered. That is, the adsorption rate of the complex was 100%, and the amount of the complex loaded onto the activated carbon was 0.81 mass%.

[0301] [Example 9] Preparation of a catalyst (catalyst 9) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (A2, granular)

[0302] 6.56 g of compound 9 was obtained by the same method as in Example 1, except that A2 (granular 5.00 g) was used for the activated carbon. The filtrate was concentrated under reduced pressure, but no solid components were recovered. That is, the adsorption rate of the complex was 100%, and the amount of complex loaded onto the activated carbon was 0.81 mass%.

[0303] [Example 10] Preparation of a catalyst (catalyst 10) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (B1 granular)

[0304] 5.84 g of compound 10 was obtained by the same method as in Example 1, except that B1 (granular, 5.00 g) was used on the activated carbon. When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 12.0 mg, so the adsorption rate of the complex was 70.5%, and the amount of complex loaded on the activated carbon was 0.57 mass%.

[0305] [Example 11] Preparation of a catalyst (catalyst 11) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (B2, granular)

[0306] 6.01 g of compound 11 was obtained by the same method as in Example 1, except that B2 (granular, 5.00 g) was used for the activated carbon. When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 12.1 mg, so the adsorption rate of the complex was 70.3%, and the amount of complex loaded onto the activated carbon was 0.57 mass%.

[0307] [Example 12] Preparation of a catalyst (catalyst 12) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (C2, granular)

[0308] 5.60 g of compound 12 was obtained by the same method as in Example 1, except that the activated carbon was changed to C2 (granular, 5.00 g). The filtrate was concentrated with an evaporator, but the solid component was not recovered. That is, the adsorption rate of the complex was 100%, and the amount of complex loaded onto the activated carbon was 0.81 mass%.

[0309] Table 3 shows the results of preparing catalysts containing Ts-DENEB catalysts adsorbed on various types of activated carbon.

[0310] Table 3: Preparation results of catalysts containing Ts-DENEB catalyst adsorbed on activated carbon

[0311] Catalyst number activated carbon Loading amount of complex on activated carbon (mass%) 1 A1 0.81 2 A2 0.80 3 B1 0.63 4 B2 0.63 5 C1 0.81 6 C2 0.80 7 M 0.81 8 A1 prize 0.81 9 A2 prize 0.81 10 B1 prize 0.57 11 B2 prize 0.57 12 C2 prize 0.81

[0312] In this way, it was possible to support Ts-DENEB complexes on various types of activated carbon.

[0313] [Example 13] Preparation of a catalyst (catalyst 13) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (A2, granular)

[0314] (R,R)-Ts-DENEB (199.9 mg, 0.307 mmol) was placed in a 200 mL branched Nas flask and nitrogen purging was performed. Subsequently, dehydrated toluene (57 mL) and dehydrated ethanol (3 mL) were added to dissolve the substance. Next, activated carbon (A2, granular, 4.96 g) manufactured by Osaka Gas Chemical Co., Ltd. was added, and the mixture was left to stand at room temperature under a nitrogen atmosphere for one week. After removing the supernatant by vacuum filtration, the filtered solid was transferred to a 300 mL beaker. Dehydrated toluene (30 mL) and dehydrated ethanol (1.5 mL) were added and stirred for one minute, after which filtration was performed. The same operation was repeated twice, and the solid component recovered by filtration was vacuum dried at 40°C for 24 hours to obtain 6.12 g of Compound 13. When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 107.0 mg, so the adsorption rate of the complex was 46.5%, and the loading amount as a complex on activated carbon was 1.9 mass%.

[0315] [Example 14] Preparation of a catalyst (catalyst 14) comprising a Ts-DENEB complex adsorbed on granular activated carbon (A2, granular)

[0316] Compound 14 was obtained in 6.20 g by the same method as in Example 13, except that the amount of Ts-DENEB introduced was changed to 400.4 mg (0.616 mmol), the amount of activated carbon A2 (granular) introduced was changed to 5.00 g, the amount of dehydrated toluene introduced was changed to 114 mL, and the amount of dehydrated ethanol introduced was changed to 6 mL. When the filtrate was concentrated by an evaporator, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 278.5 mg, so the amount of complex adsorbed onto the activated carbon was 30.4%, and the amount of complex loaded onto the activated carbon was 2.4 mass%.

[0317] [Example 15] Preparation of a catalyst (catalyst 15) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (A2, granular)

[0318] (R,R)-Ts-DENEB (199.7 mg, 0.307 mmol) was placed in a 200 mL branched Nas flask and nitrogen purging was performed. Subsequently, dehydrated methanol (60 mL) was added to dissolve it. Then, activated carbon (A2, granular, 4.87 g) from Osaka Gas Chemical Co., Ltd. was added, and the mixture was left to stand at room temperature under a nitrogen atmosphere for one week. After removing the supernatant by vacuum filtration, the filtered solid was transferred to a 300 mL beaker. Dehydrated methanol (30 mL) was added and stirred for one minute, after which filtration was performed. The same operation was repeated twice, and the solid component recovered by filtration was vacuum dried at 40°C for 24 hours to obtain 5.03 g of Compound 15. When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as the solid component. The mass of the recovered complex was 6.9 mg, so the adsorption amount of the complex onto the activated carbon was 96.5%, and the loading amount as a complex was 3.9 mass%.

[0319] [Example 16] Preparation of a catalyst (catalyst 16) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (A2, granular)

[0320] Compound 16 was obtained in an amount of 5.12 g by the same method as in Example 15, except that the amount of (R,R)-Ts-DENEB introduced was changed to 400.0 mg (0.615 mmol), the amount of activated carbon (A2, granular) introduced was changed to 4.96 g, and the amount of dehydrated methanol introduced was changed to 120 mL. When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 34.2 mg, so the amount of complex adsorbed onto the activated carbon was 91.4%, and the amount of complex loaded onto the activated carbon was 7.3 mass%.

[0321] [Example 17] Preparation of a catalyst (catalyst 17) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (C2, granular)

[0322] Compound 17 was obtained by the same method as in Example 16, except that the activated carbon was changed to C2 (granular, 4.90 g). When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 44.2 mg, so the amount of complex adsorbed onto the activated carbon was 89.0%, and the amount of complex loaded onto the activated carbon was 7.2 mass%.

[0323] [Example 18] Preparation of a catalyst (catalyst 18) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (A2, granular)

[0324] A complex solution was prepared by adding (R,R)-Ts-DENEB (400.0 mg, 0.0615 mmol) and dehydrated methanol (100 mL) to a 200 mL beaker and dissolving them. Activated carbon (A2, granular, 5.00 g) was added to a 300 mL beaker, and the complex solution was added over a period of 1 minute. The resulting suspension was allowed to stand until the solvent was removed by distillation. Dehydrated methanol (30 mL) was added to the obtained solid component and stirred for 1 minute, after which it was filtered. The same operation was repeated twice, and the solid component recovered by filtration was vacuum dried at 40°C for 24 hours to obtain 5.10 g of compound 18. The filtrate was concentrated under reduced pressure, and the unadsorbed complex was recovered as the solid component. The mass of the recovered complex was 15.7 mg, so the adsorption rate of the complex was 96.1%, and the loading amount as a complex on activated carbon was 7.7 mass%.

[0325] [Example 19] Preparation of a catalyst (catalyst 19) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (C2, granular)

[0326] Compound 19 was obtained by the same method as in Example 18, except that the activated carbon was changed to C2 (granular, 5.00 g). When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 15.1 mg, so the adsorption rate of the complex was 96.2%, and the amount of complex loaded onto the activated carbon was 7.7 mass%.

[0327] [Example 20] Preparation of a catalyst (catalyst 20) comprising a (R,R)-Ts-DENEB complex adsorbed on granular activated carbon (C2, granular)

[0328] Compound 20 was obtained by the same method as in Example 17, except that the amount of (R,R)-Ts-DENEB introduced was changed to 1200.0 mg (1.846 mmol). When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 109.4 mg, so the adsorption rate of the complex was 90.9%, and the loading amount as a complex on activated carbon was 21.8 mass%.

[0329] Table 4 shows the results of preparing catalysts containing (R,R)-Ts-DENEB complexes adsorbed on activated carbon obtained under various preparation conditions.

[0330] Table 4: Preparation results of catalysts containing (R,R)-Ts-DENEB complexes adsorbed on activated carbon obtained under various preparation conditions

[0331] Catalyst number activated carbon Solvent Concentration Preparation solvent Amount of complex introduced into activated carbon (mass%) Loading amount of complex on activated carbon (mass%) 13 A2 prize doesn't exist Toluene ethanol 4.0 1.9 14 A2 prize doesn't exist Toluene ethanol 8.0 2.4 15 A2 prize doesn't exist methanol 4.0 3.9 16 A2 prize doesn't exist methanol 8.0 7.3 18 A2 prize is available methanol 8.0 7.7 17 C2 prize doesn't exist methanol 8.0 7.2 19 C2 prize is available methanol 8.0 7.7 20 C2 prize doesn't exist methanol 24.0 21.8

[0332] In this way, by appropriately adjusting the type or concentration of the solvent, it was possible to increase the load of the complex.

[0333] <Analysis 1> Capture of ruthenium element mapping images of Catalyst 17 and Catalyst 19 by SEM-EDS

[0334] For catalysts 17 and 19, the integration time was set to 900 seconds, and SEM images and elemental mapping images targeting ruthenium were obtained using SEM-EDS. The results are shown in Fig. 4. From these elemental mapping images, it was confirmed that (R,R)-Ts-DENEB was widely dispersed on activated carbon.

[0335] <Analysis 2> Calculation of Mass Percentage of (R,R)-Ts-DENEB in Activated Carbon Surface Analysis by SEM-EDS of Catalysts 17 and 19

[0336] Surface analysis of catalysts 17 and 19 was performed using SEM-EDS. For the elements to be analyzed, a total of 12 elements were selected: 9 elements expected to be present in the activated carbon (carbon, nitrogen, oxygen, sodium, magnesium, phosphorus, potassium, calcium, and zinc) and 3 elements present in (R,R)-Ts-DENEB (sulfur, chlorine, and ruthenium). The mass percentage of (R,R)-Ts-DENEB adsorbed on the activated carbon was calculated from the mass percentage of ruthenium on the surface of the activated carbon obtained by SEM-EDS. The results are shown in Table 5.

[0337] Catalyst 17 Catalyst 19 Mass percentage of Ts-DENEB calculated by surface analysis of activated carbon 6.1 8.0

[0338] <Analysis 3> Calculation of Mass Percentage of (R,R)-Ts-DENEB by Elemental Analysis of Ashes of Catalyst 17 and Catalyst 19

[0339] Approximately 150 mg of samples of catalysts 17 and 19, each dried for 3 hours in an electric dryer set to 115°C ± 5°C and cooled for 1 hour in a desiccator (using silica gel as a desiccant), were placed in a crucible. Subsequently, the samples were placed in an electric furnace heated to 850°C and heated for 7 hours under an air atmosphere. After cooling in air, the weight of the ash was measured, and the obtained ash was analyzed by SEM-EDS using the same method as in Analysis 2 (however, in this analysis, the integration time was set to 300 seconds, and a total of 14 elements were targeted, including the 12 elements listed in Analysis 2 plus two elements that could be incorporated from the crucible: aluminum and silicon). The mass percentage of (R,R)-Ts-DENEB adsorbed on the activated carbon was calculated using the following formula. The results are shown in Table 6.

[0340] [Mathematical Formula 1]

[0341]

[0342] (W cat : Mass percentage of (R, R)-Ts-DENEB adsorbed on activated carbon

[0343] S: Mass of activated carbon (g)

[0344] R: Mass of the remainder (g)

[0345] W Ru : Mass percentage of ruthenium obtained by SEM-EDS

[0346] M: Molecular weight of (R, R)-Ts-DENEB)

[0347] Catalyst 17 Catalyst 19 Ash (mg) 2.3 3.3 W cat (mass%) 6.4 8.1

[0348] It was found that the mass percentage of (R,R)-Ts-DENEB calculated from the surface composition of the activated carbon in Analysis 2 showed good agreement with the value calculated from the ash composition in Analysis 3. From these results, it was inferred that (R,R)-Ts-DENEB is uniformly supported on the surface of the activated carbon and inside it.

[0349] [Example 21] Preparation of a catalyst (catalyst 21) comprising a chloro[(R,R)-N-[2-[2-(4-methylbenzyloxy)ethyl]amino-1,2-diphenylethyl]-p-methanesulfonamide]ruthenium(II) complex adsorbed on granular activated carbon (C2, granular)

[0350] Chloro[(R,R)-N-[2-[2-(4-methylbenzyloxy)ethyl]amino-1,2-diphenylethyl]-p-methanesulfonamide]ruthenium (II) ((R,R)-Ms-DENEB, 142.2 mg, 0.248 mmol) was added to a 200 mL branched Nas flask, and nitrogen purging was performed. Then, dehydrated methanol (48 mL) was added to dissolve it. Subsequently, activated carbon (C2, granular, 2.00 g) manufactured by Osaka Gas Chemical Co., Ltd. was added, and the mixture was left to stand at room temperature under a nitrogen atmosphere for one week. After removing the supernatant by vacuum filtration, the filtered solid was transferred to a 300 mL beaker. Dehydrated methanol (25 mL) was added and stirred for one minute, after which filtration was performed. Compound 21 was obtained by repeating the same operation twice and vacuum drying the solid component recovered by filtration at 40°C for 24 hours. When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 20.0 mg, so the amount of complex adsorbed onto activated carbon was 85.9%, and the amount of complex loaded onto activated carbon was 6.1 mass%.

[0351] [Example 22] Preparation of a catalyst (catalyst 22) comprising a chloro[(R,R)-N-[2-(3-phenylpropyl)amino-1,2-diphenylethyl]-p-toluenesulfonamide]ruthenium(II) complex adsorbed on granular activated carbon (C2, granular)

[0352] Compound 22 was obtained by the same method as in Example 21, except that the complex was changed to chloro[(R,R)-N-[2-(3-phenylpropyl)amino-1,2-diphenylethyl]-p-toluenesulfonamide]ruthenium(II) (RuCl(benz-C3-teth-(R,R)-Ts-DPEN), STREM, 153.1 mg, 0.247 mmol). When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 22.3 mg, so the amount of complex adsorbed onto the activated carbon was 85.4%, and the amount of complex loaded onto the activated carbon was 6.5 mass%.

[0353] [Example 23] Preparation of a catalyst (catalyst 23) comprising a chloro(p-cymene)[(R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II) complex adsorbed on granular activated carbon (C2, granular)

[0354] Compound 23 was obtained by the same method as in Example 21, except that the complex was changed to chloro(p-cymene)[(R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)(RuCl((R,R)-Ts-DPEN)(p-cymene), manufactured by Takasago Fragrance Industry Co., Ltd.), 157.8 mg, 0.248 mmol). When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 33.9 mg, so the amount of complex adsorbed onto the activated carbon was 78.5%, and the amount of complex loaded onto the activated carbon was 6.2 mass%.

[0355] [Example 24] Preparation of a catalyst (catalyst 24) comprising a chloro(benzene)[(R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II) complex adsorbed on granular activated carbon (C2, granular)

[0356] Compound 24 was obtained by the same method as in Example 21, except that the complex was changed to chloro(benzene[(R,R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]ruthenium(II)((R,R)-RuCl(Ts-DPEN)(benzene), manufactured by Takasago Fragrance Industry Co., Ltd., 43.3 mg, 0.247 mmol). When the filtrate was concentrated under reduced pressure, the unadsorbed complex was recovered as a solid component. The mass of the recovered complex was 29.1 mg, so the amount of complex adsorbed onto the activated carbon was 79.7%, and the amount of complex loaded onto the activated carbon was 5.7 mass%.

[0357] The results of the examination of various complexes adsorbed on activated carbon are shown in Table 7.

[0358] Table 7: Results of Immobilization Examination of Various Complexes Adsorbed on Activated Carbon

[0359] Catalyst number complex Loading amount of complex on activated carbon (mass%) 21 (R,R)-Ms-DENEB 6.1 22 RuCl(benz-C3-teth-(R,R)-Ts-DPEN) 6.5 23 RuCl((R,R)-Ts-DPEN)(p-cymen) 6.2 24 RuCl((R,R)-Ts-DPEN)(benzene) 5.7

[0360] Thus, it was found that loading onto activated carbon is not limited to Ts-DENEB but is effective for a wide range of ruthenium complexes having a diamine backbone.

[0361] [Example 25] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (Catalyst 1) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A1)

[0362] [Chemical Formula 5]

[0363]

[0364] A stirrer chip, catalyst 1 prepared in Example 1 (0.43 g, 0.005 mmol, 0.5 mol%), and potassium formate (1.68 g, 20 mmol) were added to an 80 mL shrink reaction tube, and the inside of the apparatus was purged with nitrogen. Subsequently, distilled water (5.0 mL), dehydrated ethanol (2.0 mL), and acetophenone (0.12 mL, 1.0 mmol) were added sequentially, heated to 60°C in an oil bath, and stirred at 750 rpm for 2 hours using a stirrer to prepare the target (R)-1-phenylethyl alcohol. Conversion: 89.9%, Selectivity: 100%, Optical Purity: 96.9% ee.

[0365] GC retention time (measurement condition 1); acetophenone: 2.99 min, (R)-1-phenylethanol: 5.59 min, (S)-1-phenylethanol: 6.06 min.

[0366] In addition, when the reaction solution was analyzed by ICP emission spectroscopy, 0.1% of ruthenium leaching on the activated carbon was confirmed.

[0367] [Example 26] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (catalyst 2) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2)

[0368] The target (R)-1-phenylethyl alcohol was prepared in the same manner as in Example 25, except that the catalyst 2 (0.43 g, 0.005 mmol, 0.5 mol%) prepared in Example 2 was used as the catalyst. Conversion rate: 99.0%, selectivity: 100%, optical purity: 96.9% ee (by GC analysis). Here, conversion rate is represented as ([amount of acetophenone added] - [amount of acetophenone remaining after reaction]) / [amount of acetophenone added] × 100, and selectivity is represented as ([amount of (R)-1-phenyl)ethyl alcohol produced] + [amount of (S)-1-phenylethyl alcohol produced]) / ([amount of acetophenone added] - [amount of acetophenone remaining after reaction]) × 100. In addition, when the reaction solution was analyzed by ICP emission spectroscopy, 0.2% of ruthenium leaching on the activated carbon was confirmed.

[0369] [Example 27] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (catalyst 3) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (B1)

[0370] The target (R)-1-phenylethyl alcohol was prepared in the same manner as in Example 25, except that catalyst 3 (0.55 g, 0.005 mmol, 0.5 mol%) prepared in Example 3 was used as the catalyst. Conversion rate: 96.2%, selectivity: 100%, optical purity: 96.8% ee (by GC analysis). In addition, when the reaction solution was analyzed by ICP emission analysis, 0.2% of ruthenium elution on the activated carbon was confirmed.

[0371] [Example 28] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (catalyst 4) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (B2)

[0372] The target (R)-1-phenylethyl alcohol was prepared in the same manner as in Example 25, except that the catalyst 4 (0.77 g, 0.007 mmol, 0.7 mol%) prepared in Example 4 was used as the catalyst. Conversion rate: 97.4%, selectivity: 100%, optical purity: 96.6% ee (by GC analysis). In addition, when the reaction solution was analyzed by ICP emission spectroscopy, 0.8% of ruthenium elution from the activated carbon was confirmed.

[0373] [Example 29] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (catalyst 5) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C1)

[0374] The target (R)-1-phenylethyl alcohol was prepared in the same manner as in Example 25, except that the catalyst 5 (0.43 g, 0.005 mmol, 0.5 mol%) prepared in Example 5 was used as the catalyst. (Conversion rate: 0.5%) In addition, when the reaction solution was analyzed by ICP emission spectroscopic analysis, 0.4% of ruthenium elution on the activated carbon was confirmed.

[0375] [Example 30] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (catalyst 6) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C2)

[0376] The target (R)-1-phenylethyl alcohol was prepared in the same manner as in Example 25, except that catalyst 6 (0.43 g, 0.005 mmol, 0.5 mol%) prepared in Example 6 was used as the catalyst. Conversion rate: 56.7%, selectivity: 100%, optical purity: 97.1% ee (by GC analysis). In addition, when the reaction solution was analyzed by ICP emission spectroscopy, 0.2% of ruthenium elution on the activated carbon was confirmed.

[0377] [Example 31] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (Catalyst 7) ​​containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (M)

[0378] The target (R)-1-phenylethyl alcohol was prepared in the same manner as in Example 25, except that catalyst 7 (0.43 g, 0.005 mmol, 0.5 mol%) prepared in Example 7 was used as the catalyst. Conversion rate: 95.7%, selectivity: 100%, optical purity: 96.3% ee (by GC analysis). In addition, when the reaction solution was analyzed by ICP emission spectroscopy, 0.2% of ruthenium elution on the activated carbon was confirmed.

[0379] [Comparative Example 1] Preparation of (R)-1-phenylethyl alcohol by hydrogen transfer reaction of acetophenone using (R,R)-Ts-DENEB

[0380] The target (R)-1-phenylethyl alcohol was prepared by the same method as in Example 25, except that Ts-DENEB (3.3 mg, 0.005 mmol, 0.5 mol%) was used as the catalyst. Conversion: 93.5%, selectivity: 100%, optical purity: 94.4% ee (by GC analysis).

[0381] Table 8 shows the results of activity tests on various activated carbon-supported catalysts and homogeneous catalysts shown in Examples 25 to 31 and Comparative Example 1.

[0382] Table 8: Activity test results of various catalysts and homogeneous catalysts

[0383] Catalyst number or abbreviation used Activated carbon used Turnover rate (%) Optical purity (%ee) Ruthenium leaching amount (%) Example 25 1 A1 89.9 96.9 0.1 Example 26 2 A2 99.0 96.9 0.2 Example 27 3 B1 96.2 96.8 0.2 Example 28 4 B2 97.4 96.6 0.8 Example 29 5 C1 0.5 － 0.4 Example 30 6 C2 56.7 97.1 0.2 Example 31 7 M 95.7 96.3 0.2 Comparative Example 1 Ts-DENEB - 93.5 94.4 －

[0384] As such, it was found that the activated carbon-supported Ts-DENEB catalyst possesses high catalytic activity comparable to that of a homogeneous catalyst, and that almost no leaching of ruthenium into the reaction solution was observed.

[0385] [Example 32] Measurement of changes over time in the hydrogen transfer reaction of acetophenone using a catalyst (Catalyst 3) containing a ruthenium complex absorbed by activated carbon

[0386] [Chemical Formula 6]

[0387]

[0388] A stirrer chip, catalyst 3 prepared in Example 3 (0.17 g, 0.016 mmol, 0.16 mol%), and potassium formate (1.68 mmol, 1.68 g, 20 mmol) were added to an 80 mL shrink tube, and the inside of the apparatus was purged with nitrogen. Subsequently, distilled water (5.0 mL), dehydrated ethanol (2.0 mL), and acetophenone (0.12 mL, 1.0 mmol) were added sequentially, heated to 60°C in an oil bath, and stirred at 750 rpm for 5 hours using a stirrer. 0.1 mL of the suspension during heating was taken with a syringe, and the change in conversion rate over time was measured. The results are shown in Figure 1.

[0389] [Example 33] Thermal filtration test in the non-hydrogen transfer reaction of acetophenone using a catalyst (Catalyst 3) containing a Ts-DENEB complex adsorbed on activated carbon

[0390] Two 80 mL shrink tubes were prepared, and a stirrer chip was placed in one, and a glass filter equipped with glass fiber filter paper was installed. In the other, the stirrer chip, catalyst 3 prepared in Example 3 (0.17 g, 0.016 mmol, 0.16 mol%), and potassium formate (1.68 mmol, 1.68 g, 20 mmol) were added. Subsequently, the inside of each apparatus was purged with nitrogen. Distilled water (5.0 mL), ethanol (2.0 mL), and acetophenone (0.12 mL, 1.0 mmol) were then sequentially added into the shrink tube containing the reagents. Each shrink tube was heated to 60°C in an oil bath and stirred at 750 rpm using a stirrer. One hour after the start of heating and stirring, the suspension was transferred to a pre-prepared 80 mL shrink tube using a cannula, and the liquid components were filtered into the shrink tube under nitrogen. Thereafter, heating and stirring were continued at 60°C. 0.1 mL of the reaction solution during heating was taken with a syringe, and the change in conversion rate over time was measured. The trend of the conversion rate is shown in Fig. 2 along with the results of Example 32.

[0391] As shown in Figure 2, the reaction is completely stopped when the solid component is removed during the heating reaction. That is, in this catalytic reaction, it was found that the complex adsorbed on the activated carbon is functioning, rather than the complex eluted to the liquid component.

[0392] [Example 34] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (Catalyst 8) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A1, granular)

[0393] [Chemical Formula 7]

[0394]

[0395] [Reaction (1st reaction)]

[0396] A 50 mL four-necked round-bottom flask was equipped with a mechanical stirrer, a condenser, a thermometer, and a three-way stopcock. Catalyst 8 (0.86 g, 0.01 mmol, 0.5 mol%) prepared in Example 8 and potassium formate (3.36 g, 40 mmol) were added, and the inside of the apparatus was purged with nitrogen. Subsequently, distilled water (10 mL), ethanol (5.0 mL), and acetophenone (0.23 mL, 2.0 mmol) were added sequentially. The mixture was heated to 60°C in an oil bath and stirred at 250 rpm for 2.5 hours using a mechanical stirrer to produce the target (R)-1-phenylethyl alcohol. Conversion: 98.3%, Selectivity: 100%, Optical Purity: 97.2% ee (by GC analysis). In addition, to show changes over time, data from the case of a 1-hour reaction (stirring) were also collected.

[0397] [Preparation of Catalyst Cleaning Solution]

[0398] 67.20 g of potassium formate was placed in a 500 mL branched Nas flask and the interior was purged with nitrogen. 200 mL of distilled water and 100 mL of dehydrated ethanol were added sequentially, and the potassium formate was dissolved to prepare a catalyst washing solution.

[0399] [Catalyst Reuse Operation (2nd Reaction)]

[0400] After the reaction was complete, stirring was stopped, and the supernatant was removed using a syringe. The solid components were washed twice with 5 mL of the prepared catalyst wash, and Compound 8 was recovered. Potassium formate (1.68 g, 40 mmol) was added to this flask, and the inside of the apparatus was purged with nitrogen. Subsequently, distilled water (10 mL), dehydrated ethanol (5.0 mL), and acetophenone (0.23 mL, 2.0 mmol) were added sequentially, heated to 60°C in an oil bath, and stirred for 2.5 hours using a mechanical stirrer to prepare the target (R)-1-phenylethyl alcohol. Conversion rate: 99.0%, selectivity: 100%, optical purity: 96.6% ee (by GC analysis). In addition, to show changes over time, data from a reaction (stirring) of 1 hour were also collected.

[0401] [Catalyst Reuse Operation (Reaction after the 3rd time)]

[0402] After the second reaction, the catalyst was reused through the same operation.

[0403] The conversion rate, optical purity, and ruthenium leaching amount of each reaction are as shown in Table 9.

[0404] Table 9: Conversion rate, optical purity, and ruthenium elution amount of each reaction in Example 34

[0405] Reaction time (time) Turnover rate (%) Optical purity (ee %) Ruthenium leaching amount (%) Experiment 1 1st reaction 1 57.5 97.0 - 2.5 98.3 97.2 0.4 Experiment 2 2nd reaction 1 83.3 96.4 - 2.5 99.0 96.6 0.1 Experiment 3 3rd reaction 1 78.4 96.7 - 2.5 98.1 96.8 0.1 Experiment 4 4th reaction 1 77.1 96.8 - 2.5 96.5 96.5 0.3 Experiment 5 5th reaction 1 76.9 96.4 - 2.5 96.4 96.4 < 0.1

[0406] [Example 35] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (Catalyst 9) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2, granular)

[0407] The target (R)-1-phenylethyl alcohol was prepared by the same procedure as in Example 34, except that catalyst 9 (0.86 g, 0.01 mmol, 0.5 mol%) was used as the catalyst and the heating and stirring time was changed to 2 hours. Conversion: 99.4%, selectivity: 100%, optical purity: 97.0% ee (according to GC analysis).

[0408] In addition, the target (R)-1-phenylethyl alcohol was prepared by performing the preparation and reuse operation of the catalyst washing solution under the same conditions as in Example 34 (except that the heating and stirring time in this example was 2 hours). The conversion rate, optical purity, and ruthenium elution amount of each reaction are as shown in Table 10.

[0409] Table 10: Conversion rate, optical purity, and ruthenium elution amount of each reaction in Example 35

[0410] Reaction time (time) Turnover rate (%) Optical purity (ee %) Ruthenium leaching amount (%) Experiment 1 1st reaction 1 84.8 96.9 - 2 99.4 97.0 0.5 Experiment 2 2nd reaction 1 90.2 97.1 - 2 99.0 96.7 < 0.1 Experiment 3 3rd reaction 1 85.5 96.2 - 2 98.7 96.8 < 0.1 Experiment 4 4th reaction 1 86.3 96.6 - 2 97.6 96.5 < 0.1 Experiment 5 5th reaction 1 82.9 96.8 - 2 95.2 96.5 < 0.1

[0411] [Example 36] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (catalyst 10) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (B1, granular)

[0412] The target (R)-1-phenylethyl alcohol was prepared by the same procedure as in Example 34, except that catalyst 10 (1.22 g, 0.01 mmol, 0.5 mol%) was used as the catalyst. Conversion: 97.5%, selectivity: 100%, optical purity: 97.0% ee (according to GC analysis).

[0413] In addition, the target (R)-1-phenylethyl alcohol was prepared by performing the preparation and reuse operation of the catalyst washing solution under the same conditions as in Example 34 (except that the heating and stirring time in this example was 2 hours). The conversion rate, optical purity, and ruthenium elution amount of each reaction are as shown in Table 11.

[0414] Table 11: Conversion rate, optical purity, and ruthenium elution amount of each reaction in Example 36

[0415] Reaction time (time) Turnover rate (%) Optical purity (ee %) Ruthenium leaching amount (%) Experiment 1 1st reaction 1 65.6 97.3 - 2.5 97.5 97.0 1.2 Experiment 2 2nd reaction 1 79.3 96.9 - 2 95.9 96.7 0.7 Experiment 3 3rd reaction 1 80.0 96.2 - 2 95.6 96.3 0.4 Experiment 4 4th reaction 1 72.9 96.5 - 2 89.0 96.1 0.2 Experiment 5 5th reaction 1 77.5 96.4 - 2 90.3 96.4 0.2

[0416] [Example 37] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (catalyst 11) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (B2, granular)

[0417] The target (R)-1-phenylethyl alcohol was prepared by the same procedure as in Example 34, except that catalyst 11 (1.22 g, 0.01 mmol, 0.5 mol%) was used as the catalyst and the heating and stirring time was changed to 2 hours. Conversion: 96.9%, selectivity: 100%, optical purity: 96.7% ee (according to GC analysis).

[0418] In addition, the target (R)-1-phenylethyl alcohol was prepared by performing the preparation and reuse of the catalyst washing solution under the same conditions as in Example 34 (except that the heating and stirring time in this example was 2 hours). The conversion rate, optical purity, and ruthenium elution amount of each reaction are as shown in Table 12.

[0419] Table 12: Conversion rate, optical purity, and ruthenium elution amount of each reaction in Example 37

[0420] Reaction time (time) Turnover rate (%) Optical purity (ee %) Ruthenium leaching amount (%) Experiment 1 1st reaction 1 76.1 96.9 - 2 96.9 96.7 < 0.1 Experiment 2 2nd reaction 1 88.3 96.6 - 2 96.6 96.4 < 0.1 Experiment 3 3rd reaction 1 82.9 96.5 - 2 95.6 96.2 < 0.1 Experiment 4 4th reaction 1 77.6 96.2 - 2 93.0 96.3 < 0.1 Experiment 5 5th reaction 1 75.1 96.0 - 2 90.0 95.7 < 0.1 Experiment 6 6th reaction 1 67.4 96.3 - 2 87.0 96.3 < 0.1

[0421] [Example 38] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (catalyst 15) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2, granular)

[0422] The target (R)-1-phenylethyl alcohol was prepared by the same procedure as in Example 34, except that catalyst 15 (171.1 mg, 0.01 mmol, 0.5 mol%) was used as the catalyst and the heating and stirring time was changed to 2 hours. Conversion: 99.7%, selectivity: 100%, optical purity: 97.1% ee (according to GC analysis).

[0423] In addition, the target (R)-1-phenylethyl alcohol was prepared by preparing and reusing the catalyst washing solution under the same conditions as in Example 34 (except that the heating and stirring time in this example was 2 hours). The conversion rate, optical purity, and ruthenium elution amount of each reaction are as shown in Table 13.

[0424] Table 13: Conversion rate, optical purity, and ruthenium elution amount of each reaction in Example 38

[0425] Reaction time (time) Turnover rate (%) Optical purity (ee %) Ruthenium leaching amount (%) Experiment 1 1st reaction 1 75.7 97.2 - 2 99.7 97.1 < 0.1 Experiment 2 2nd reaction 1 78.6 97.1 - 2 99.9 96.9 < 0.1 Experiment 3 3rd reaction 1 78.1 97.0 - 2 99.5 96.9 < 0.1 Experiment 4 4th reaction 1 78.5 96.9 - 2 99.5 96.7 < 0.1 Experiment 5 5th reaction 1 72.5 96.8 - 2 98.8 97.0 < 0.1 Experiment 6 6th reaction 1 71.0 97.0 - 2 98.5 95.9 < 0.1 Experiment 7 7th reaction 1 64.5 96.9 - 2 97.6 96.4 < 0.1

[0426] [Example 39] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (Catalyst 16) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2, granular)

[0427] The target (R)-1-phenylethyl alcohol was prepared by the same procedure as in Example 34, except that catalyst 16 (97.0 mg, 0.01 mmol, 0.5 mol%) was used as the catalyst and the heating and stirring time was changed to 3 hours. Conversion: 99.2%, selectivity: 100%, optical purity: 96.9% ee (according to GC analysis).

[0428] In addition, the target (R)-1-phenylethyl alcohol was prepared by preparing and reusing the catalyst washing solution under the same conditions as in Example 34 (except that the heating and stirring time in this example was 3 hours). The conversion rate, optical purity, and ruthenium elution amount of each reaction are as shown in Table 14.

[0429] Table 14: Conversion rate, optical purity, and ruthenium elution amount of each reaction in Example 39

[0430] Reaction time (time) Turnover rate (%) Optical purity (ee %) Ruthenium leaching amount (%) Experiment 1 1st reaction 1 39.8 96.2 - 3 99.2 96.9 < 0.1 Experiment 2 2nd reaction 1 53.1 97.2 - 3 99.8 97.1 < 0.1 Experiment 3 3rd reaction 1 53.8 97.2 - 3 99.5 97.0 < 0.1 Experiment 4 4th reaction 1 56.1 96.3 - 2.5 97.9 97.1 < 0.1 Experiment 5 5th reaction 1 50.6 96.7 - 3 99.4 96.8 < 0.1 Experiment 6 6th reaction 1 51.8 96.8 - 3 99.5 97.0 < 0.1 Experiment 7 7th reaction 1 47.4 96.9 - 3 99.6 96.9 < 0.1

[0431] [Example 40] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (Catalyst 17) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C2, granular)

[0432] The target (R)-1-phenylethyl alcohol was prepared by the same procedure as in Example 34, except that catalyst 17 (90.9 mg, 0.01 mmol, 0.5 mol%) was used as the catalyst. Conversion: 99.7%, selectivity: 100%, optical purity: 97.7% ee (according to GC analysis).

[0433] In addition, the target (R)-1-phenylethyl alcohol was prepared by preparing and reusing the catalyst washing solution under the same conditions as in Example 34 (except in this example where the heating and stirring time was 3 hours). The conversion rate, optical purity, and ruthenium elution amount of each reaction are as shown in Table 15.

[0434] Table 15: Conversion rate, optical purity, and ruthenium elution amount of each reaction in Example 40

[0435] Reaction time (time) Turnover rate (%) Optical purity (ee %) Ruthenium leaching amount (%) Experiment 1 1st reaction 1 68.2 97.6 - 2.5 99.9 97.7 < 0.1 Experiment 2 2nd reaction 1 62.3 97.5 - 2.5 99.7 97.6 < 0.1 Experiment 3 3rd reaction 1 57.9 97.5 - 3 99.0 97.6 0.1 Experiment 4 4th reaction 1 40.0 97.2 - 3 97.1 97.6 < 0.1 Experiment 5 5th reaction 1 42.7 97.0 - 3 96.0 97.4 < 0.1

[0436] As such, it was found that the activated carbon-supported ruthenium complex of the present invention maintains high catalytic activity even with respect to reuse after catalyst recovery. Furthermore, it was found that the amount of ruthenium eluted into each reaction solution was extremely small, and that the ruthenium complex was firmly supported on the activated carbon.

[0437] [Example 41] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (catalyst 20) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C2, granular)

[0438] (Target (R)-1-phenylethyl alcohol was prepared by the same procedure as in Example 34, except that 20g of catalyst (36.3 mg, 0.01 mmol, 0.5 mol%) was used and the heating and stirring time was changed to 2 hours. Conversion: 100.0%, selectivity: 100%, optical purity: 97.5% ee (according to GC analysis).

[0439] In addition, the target (R)-1-phenylethyl alcohol was prepared by preparing and reusing the catalyst washing solution under the same conditions as in Example 34 (except in this example where the heating and stirring time was 3 hours). The conversion rate, optical purity, and ruthenium elution amount of each reaction are as shown in Table 16.

[0440] Table 16: Conversion rate, optical purity, and ruthenium elution amount of each reaction in Example 41

[0441] Reaction time (time) Turnover rate (%) Optical purity (ee %) Ruthenium leaching amount (%) Experiment 1 1st reaction 1 77.5 97.2 - 2 100.0 97.5 5.0 Experiment 2 2nd reaction 1 54.3 97.3 - 2 92.9 97.5 2.2

[0442] As is evident from the comparison between Example 40 and Example 41, when the amount of (R,R)-Ts-DENEB complex adsorbed onto activated carbon is increased, the amount of ruthenium leached after the reaction tends to increase. Therefore, from the perspective of practicality, it is preferable that the total mass of the (R,R)-Ts-DENEB complex adsorbed be 25 mass% or less relative to the total mass of the activated carbon.

[0443] [Example 42] Preparation of (R)-1-phenylethyl alcohol by a hydrogen transfer reaction of acetophenone using a catalyst (Catalyst 21) containing a (R,R)-Ms-DENEB complex (manufactured by Takasago Fragrance Industry Co., Ltd.) adsorbed on activated carbon (C2, granular)

[0444] The target (R)-1-phenylethyl alcohol was prepared by the same procedure as in Example 34, except that catalyst 21 (100.7 mg, 0.01 mmol, 0.5 mol%) was used as the catalyst. Conversion: 100%, selectivity: 100%, optical purity: 96.6% ee (according to GC analysis).

[0445] In addition, the target (R)-1-phenylethyl alcohol was prepared by preparing and reusing the catalyst washing solution under the same conditions as in Example 34 (except that the heating and stirring time in this example was 2 hours). The conversion rate, optical purity, and ruthenium elution amount of each reaction are as shown in Table 17.

[0446] Table 17: Conversion rate, optical purity, and ruthenium elution amount of each reaction in Example 42

[0447] Reaction time (time) Turnover rate (%) Optical purity (ee %) Ruthenium leaching amount (%) Experiment 1 1st reaction 1 69.6 96.8 - 2.5 100 96.6 < 0.1 Experiment 2 2nd reaction 1 57.5 96.3 - 2 91.2 96.3 -

[0448] As shown in Table 17, it was found that Ms-DENEB, which has the same tether structure as Ts-DENEB, has high reusability because there is no leaching of ruthenium into the reaction solution when supported on activated carbon.

[0449] [Example 43] Preparation of (R)-1-phenylethyl alcohol by auxiliary hydrogen transfer reaction of acetophenone using a catalyst (Catalyst 23) containing a RuCl((R,R)-Ts-DPEN)(p-cymen) complex adsorbed on activated carbon (C2, granular)

[0450] The target (R)-1-phenylethyl alcohol was prepared by the same procedure as in Example 34, except that catalyst 23 (120.0 mg, 0.01 mmol, 0.5 mol%) was used as the catalyst. Conversion: 94.3%, selectivity: 100%, optical purity: 94.8% ee (according to GC analysis).

[0451] In addition, the target (R)-1-phenylethyl alcohol was prepared by preparing and reusing the catalyst washing solution under the same conditions as in Example 34 (except that the heating and stirring time in this example was 2 hours). The conversion rate, optical purity, and ruthenium elution amount of each reaction are as shown in Table 18.

[0452] Table 18: Conversion rate, optical purity, and ruthenium elution amount of each reaction in Example 43

[0453] Reaction time (time) Turnover rate (%) Optical purity (ee %) Ruthenium leaching amount (%) Experiment 1 1st reaction 1 55.8 94.6 - 2.5 94.3 94.8 < 0.1 Experiment 2 2nd reaction 1 28.1 93.8 - 2 51.9 94.3 -

[0454] As shown in Table 18, it was found that even RuCl((R,R)-Ts-DPEN)(p-cymen), a general-purpose complex effective for hydrogen transfer reactions, has moderate reusability because there is no leaching of ruthenium into the reaction solution when supported on activated carbon.

[0455] Next, the effect on reaction conversion rate and optical purity in the production of (R)-1-phenylethyl alcohol by the hydrogen transfer reaction of acetophenone attributable to the catalyst of the present invention was compared with the following Comparative Examples 2 and 3. The results are shown in Table 19.

[0456] [Comparative Example 2] Preparation of (R)-1-phenylethyl alcohol by hydrogen transfer reaction of acetophenone using (R,R)-Ts-DENEB complex

[0457] A stirrer chip was placed in an 80 mL shrink reaction tube, Ts-DENEB (6.5 mg, 0.01 mmol, 0.5 mol%) and potassium formate (3.36 g, 40 mmol) were added, and the inside of the apparatus was purged with nitrogen. Subsequently, distilled water (10 mL), ethanol (5.0 mL), and acetophenone (0.23 mL, 2.0 mmol) were added sequentially, heated to 60°C in an oil bath, and stirred at 750 rpm for 2.5 hours using a stirrer to prepare the target (R)-1-phenylethyl alcohol. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 19.

[0458] [Comparative Example 3] Preparation of (R)-1-phenylethyl alcohol by non-hydrogen transfer reaction of acetophenone using (R,R)-Ts-DENEB complex in the presence of formic acid-triethylamine

[0459] A stirrer chip was placed in an 80 mL shrink reaction tube, (R,R)-Ts-DENEB (6.5 mg, 0.01 mmol, 0.5 mol%) was added, and the inside of the apparatus was purged with nitrogen. Subsequently, acetophenone (0.23 mL, 2.0 mmol) and a formic acid-triethylamine mixed solution (5:2, 2.0 mL, 20 mmol) were added sequentially, heated to 60°C in an oil bath, and stirred at 750 rpm for 1 hour using a stirrer to prepare the target (R)-1-phenylethyl alcohol. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 19.

[0460] Table 19: Reaction conversion rate and optical purity calculated from GC analysis results

[0461] catalyst menstruum reducing agent Reaction time (time) Turnover rate (%) Optical purity (% ee) Example 41 Ts-DENEB / Activated Carbon C2 (Granular) Water-ethanol potassium formate 2.5 99.9 97.7 Example 39 Ts-DENEB / Activated Carbon A2 (Granular) Water-ethanol potassium formate 3 99.2 96.9 Comparative Example 2 Ts-DENEB Water-ethanol potassium formate 2.5 97.8 93.0 Comparative Example 3 Ts-DENEB doesn't exist formic acid-triethylamine 1 96.6 96.1

[0462] The effects on reaction conversion rate and optical purity in the production of (R)-1-(4'-chlorophenyl)ethanol by the hydrogen transfer reaction of 4'-chloroacetophenone attributable to the catalyst of the present invention were examined. The results are shown in Table 20.

[0463] [Example 44] Preparation of (R)-1-(4'-chlorophenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-chloroacetophenone using a catalyst (Catalyst 17) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C2, granular)

[0464] The target (R)-1-(4'-chlorophenyl)ethanol was prepared by the same operation as in Example 40, except that 4'-chloroacetophenone (0.31 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 20.

[0465] GC retention time (measurement condition 2); 4'-chloroacetophenone: 7.36 min, (R)-1-(4'-chlorophenyl) )ethanol: 19.58 min, (S)-1-(4'-chlorophenyl)ethanol: 22.76 min.

[0466] [Example 45] Preparation of (R)-1-(4'-chlorophenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-chloroacetophenone using a catalyst (Catalyst 16) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2, granular)

[0467] The target (R)-1-(4'-chlorophenyl)ethanol was prepared by the same operation as in Example 39, except that 4'-chloroacetophenone (0.31 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 20.

[0468] [Comparative Example 4] Preparation of (R)-1-(4'-chlorophenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-chloroacetophenone using (R,R)-Ts-DENEB complex

[0469] The target (R)-1-(4'-chlorophenyl)ethanol was prepared by the same operation as Comparative Example 2, except that 4'-chloroacetophenone (0.31 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 20.

[0470] [Comparative Example 5] Preparation of (R)-1-(4'-chlorophenyl)ethanol by non-hydrogen transfer reaction of 4'-chloroacetophenone using (R,R)-Ts-DENEB complex in the presence of formic acid-triethylamine

[0471] The target (R)-1-(4'-chlorophenyl)ethanol was prepared by the same operation as Comparative Example 3, except that 4'-chloroacetophenone (0.31 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 3 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 20.

[0472] Table 20: Reaction conversion rate and optical purity calculated from GC analysis results

[0473] catalyst menstruum reducing agent Reaction time (time) Turnover rate (%) Optical purity (% ee) Example 44 Ts-DENEB / Activated Carbon C2 (Granular) Water-ethanol potassium formate 5 99.3 93.5 Example 45 Ts-DENEB / Activated Carbon A2 (Granular) Water-ethanol potassium formate 5 99.1 90.4 Comparative Example 4 Ts-DENEB Water-ethanol potassium formate 5 99.8 91.3 Comparative Example 5 Ts-DENEB doesn't exist formic acid-triethylamine 3 99.8 91.8

[0474] The effects on reaction conversion rate and optical purity in the production of (R)-1-(2'-chlorophenyl)ethanol by the auxiliary hydrogen transfer reaction of 2'-chloroacetophenone attributable to the catalyst of the present invention were examined. The results are shown in Table 21.

[0475] [Example 46] Preparation of (R)-1-(2'-chlorophenyl)ethanol by auxiliary hydrogen transfer reaction of 2'-chloroacetophenone using a catalyst (Catalyst 17) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C2, granular)

[0476] The target (R)-1-(2'-chlorophenyl)ethanol was prepared by the same procedure as in Example 40, except that 2'-chloroacetophenone (0.31 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 21.

[0477] GC retention time (measurement condition 2); 2'-chloroacetophenone: 5.08 min, (R)-1-(2'-chlorophenyl)ethanol: 17.97 min, (S)-1-(2'-chlorophenyl)ethanol: 24.83 min.

[0478] [Example 47] Preparation of (R)-1-(2'-chlorophenyl)ethanol by auxiliary hydrogen transfer reaction of 2'-chloroacetophenone using a catalyst (Catalyst 16) containing a (A2, granular)(R,R)-Ts-DENEB complex adsorbed on activated carbon

[0479] The target (R)-1-(2'-chlorophenyl)ethanol was prepared by the same procedure as in Example 39, except that 2'-chloroacetophenone (0.31 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 21.

[0480] [Comparative Example 6] Preparation of (R)-1-(2'-chlorophenyl)ethanol by non-hydrogen transfer reaction of 2'-chloroacetophenone using (R,R)-Ts-DENEB complex

[0481] The target (R)-1-(2'-chlorophenyl)ethanol was prepared by the same operation as Comparative Example 2, except that 2'-chloroacetophenone (0.31 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 21.

[0482] [Comparative Example 7] Preparation of (R)-1-(2'-chlorophenyl)ethanol by non-hydrogenation reaction of 2'-chloroacetophenone using (R,R)-Ts-DENEB complex in the presence of formic acid-triethylamine

[0483] The target (R)-1-(2'-chlorophenyl)ethanol was prepared by the same procedure as Comparative Example 3, except that 2'-chloroacetophenone (0.31 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 3 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 21.

[0484] Table 21: Reaction conversion rate and optical purity calculated from GC analysis results

[0485] catalyst menstruum reducing agent Reaction time (time) Turnover rate (%) Optical purity (% ee) Example 46 Ts-DENEB / Activated Carbon C2 (Granular) Water-ethanol potassium formate 5 99.7 90.3 Example 47 Ts-DENEB / Activated Carbon A2 (Granular) Water-ethanol potassium formate 5 99.4 85.0 Comparative Example 6 Ts-DENEB Water-ethanol potassium formate 5 98.3 79.1 Comparative Example 7 Ts-DENEB doesn't exist formic acid-triethylamine 3 97.6 86.3

[0486] The effects on reaction conversion rate and optical purity in the production of (R)-1-(4'-methoxyphenyl)ethanol by the auxiliary hydrogen transfer reaction of 4'-methoxyacetophenone attributable to the catalyst of the present invention were examined. The results are shown in Table 22.

[0487] [Example 48] Preparation of (R)-1-(4'-methoxyphenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-methoxyacetophenone using (R,R)-Ts-DENEB complex (Catalyst 17) adsorbed on activated carbon (C2, granular)

[0488] The target (R)-1-(4'-methoxyphenyl)ethanol was prepared by the same procedure as in Example 40, except that 4'-methoxyacetophenone (0.30 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 22.

[0489] GC retention time (measurement condition 2); 4'-methoxyacetophenone: 12.65 min, (R)-1-(4'-methoxyphenyl)ethanol: 19.09 min, (S)-1-(4'-methoxyphenyl)ethanol: 20.76 min.

[0490] [Example 49] Preparation of (R)-1-(4'-methoxyphenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-methoxyacetophenone using a catalyst (Catalyst 16) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2, granular)

[0491] The target (R)-1-(4'-methoxyphenyl)ethanol was prepared by the same procedure as in Example 39, except that 4'-methoxyacetophenone (0.30 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 22.

[0492] [Comparative Example 8] Preparation of (R)-1-(4'-methoxyphenyl)ethanol by non-hydrogen transfer reaction of 4'-methoxyacetophenone using (R,R)-Ts-DENEB complex

[0493] The target (R)-1-(4'-methoxyphenyl)ethanol was prepared by the same operation as Comparative Example 2, except that 4'-methoxyacetophenone (0.30 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 22.

[0494] [Comparative Example 9] Preparation of (R)-1-(4'-methoxyphenyl)ethanol by non-hydrogenation reaction of 4'-methoxyacetophenone using (R,R)-Ts-DENEB complex in the presence of formic acid-triethylamine

[0495] The target (R)-1-(4'-methoxyphenyl)ethanol was prepared by the same procedure as Comparative Example 3, except that 4'-methoxyacetophenone (0.30 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 3 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 22.

[0496] Table 22: Reaction conversion rate and optical purity calculated from GC analysis results

[0497] catalyst menstruum reducing agent Reaction time (time) Turnover rate (%) Optical purity (% ee) Example 48 Ts-DENEB / Activated Carbon C2 (Granular) Water-ethanol potassium formate 5 99.0 95.1 Example 49 Ts-DENEB / Activated Carbon A2 (Granular) Water-ethanol potassium formate 5 96.4 89.8 Comparative Example 8 Ts-DENEB Water-ethanol potassium formate 5 85.5 91.8 Comparative Example 9 Ts-DENEB doesn't exist formic acid-triethylamine 3 94.1 96.0

[0498] The effects on reaction conversion rate and optical purity in the production of (R)-1-(2'-methoxyphenyl)ethanol by the auxiliary hydrogen transfer reaction of 2'-methoxyacetophenone attributable to the catalyst of the present invention were examined. The results are shown in Table 23.

[0499] [Example 50] Preparation of (R)-1-(2'-methoxyphenyl)ethanol by auxiliary hydrogen transfer reaction of 2'-methoxyacetophenone using a catalyst (Catalyst 17) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C2, granular)

[0500] The target (R)-1-(2'-methoxyphenyl)ethanol was prepared by the same procedure as in Example 40, except that 2'-methoxyacetophenone (0.30 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 23.

[0501] GC retention time (measurement condition 2); 2'-methoxyacetophenone: 7.90 min, (R)-1-(2'-methoxyphenyl)ethanol: 18.29 min, (S)-1-(2'-methoxyphenyl)ethanol: 16.78 min.

[0502] [Example 51] Preparation of (R)-1-(2'-methoxyphenyl)ethanol by auxiliary hydrogen transfer reaction of 2'-methoxyacetophenone using a catalyst (Catalyst 16) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2, granular)

[0503] The target (R)-1-(2'-methoxyphenyl)ethanol was prepared by the same procedure as in Example 39, except that 2'-methoxyacetophenone (0.30 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 23.

[0504] [Comparative Example 10] Preparation of (R)-1-(2'-methoxyphenyl)ethanol by auxiliary hydrogen transfer reaction of 2'-methoxyacetophenone using (R,R)-Ts-DENEB complex

[0505] The target (R)-1-(2'-methoxyphenyl)ethanol was prepared by the same operation as Comparative Example 2, except that 2'-methoxyacetophenone (0.30 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 23.

[0506] [Comparative Example 11] Preparation of (R)-1-(2'-methoxyphenyl)ethanol by non-hydrogenation reaction of 2'-methoxyacetophenone using (R,R)-Ts-DENEB complex in the presence of formic acid-triethylamine

[0507] The target (R)-1-(2'-methoxyphenyl)ethanol was prepared by the same operation as Comparative Example 3, except that 2'-methoxyacetophenone (0.30 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 23.

[0508] Table 23: Reaction conversion rate and optical purity calculated from GC analysis results

[0509] catalyst menstruum reducing agent Reaction time (time) Turnover rate (%) Optical purity (% ee) Example 50 Ts-DENEB / Activated Carbon C2 (Granular) Water-ethanol potassium formate 5 99.8 96.6 Example 51 Ts-DENEB / Activated Carbon A2 (Granular) Water-ethanol potassium formate 5 93.0 95.1 Comparative Example 10 Ts-DENEB Water-ethanol potassium formate 5 80.0 87.3 Comparative Example 11 Ts-DENEB doesn't exist formic acid-triethylamine 3 94.6 94.0

[0510] The effects on reaction conversion rate and optical purity in the production of (R)-1-(4'-trifluoromethylphenyl)ethanol by the hydrogen transfer reaction of 4'-trifluoromethylacetophenone attributable to the catalyst of the present invention were examined. The results are shown in Table 24.

[0511] [Example 52] Preparation of (R)-1-(4'-trifluoromethylphenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-trifluoromethylacetophenone using a catalyst (Catalyst 17) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C2, granular)

[0512] The target (R)-1-(4'-trifluoromethylphenyl)ethanol was prepared by the same operation as in Example 40, except that 4'-trifluoromethylacetophenone (0.38 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 24.

[0513] GC retention time (measurement condition 1); 4'-trifluoromethylacetophenone: 3.09 min, (R)-1-(4'-trifluoromethylphenyl)ethanol: 10.18 min, (S)-1-(4'-trifluoromethylphenyl)ethanol: 13.03 min.

[0514] [Example 53] Preparation of (R)-1-(4'-trifluoromethylphenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-trifluoromethylacetophenone using a catalyst (Catalyst 16) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2, granular)

[0515] The target (R)-1-(4'-trifluoromethylphenyl)ethanol was prepared by the same operation as in Example 39, except that 4'-trifluoromethylacetophenone (0.38 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 24.

[0516] [Comparative Example 12] Preparation of (R)-1-(4'-trifluoromethylphenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-trifluoromethylacetophenone using (R,R)-Ts-DENEB complex

[0517] The target (R)-1-(4'-trifluoromethylphenyl)ethanol was prepared by the same operation as Comparative Example 2, except that 4'-trifluoromethylacetophenone (0.38 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 24.

[0518] [Comparative Example 13] Preparation of (R)-1-(4'-trifluoromethylphenyl)ethanol by non-hydrogen transfer reaction of 4'-trifluoromethylacetophenone using (R,R)-Ts-DENEB complex in the presence of formic acid-triethylamine

[0519] The target (R)-1-(4'-trifluoromethylphenyl)ethanol was prepared by the same operation as Comparative Example 3, except that 4'-trifluoromethylacetophenone (0.38 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 3 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 24.

[0520] Table 24: Reaction conversion rate and optical purity calculated from GC analysis results

[0521] catalyst menstruum reducing agent Reaction time (time) Turnover rate (%) Optical purity (% ee) Example 52 Ts-DENEB / Activated Carbon C2 (Granular) Water-ethanol potassium formate 5 100 88.2 Example 53 Ts-DENEB / Activated Carbon A2 (Granular) Water-ethanol potassium formate 5 85 79.5 Comparative Example 12 Ts-DENEB Water-ethanol potassium formate 5 100 91.7 Comparative Example 13 Ts-DENEB doesn't exist formic acid-triethylamine 5 99.6 91.7

[0522] The effects on reaction conversion rate and optical purity in the production of (R)-1-(4'-cyanophenyl)ethanol by the auxiliary hydrogen transfer reaction of 4'-cyanoacetophenone attributable to the catalyst of the present invention were examined. The results are shown in Table 25.

[0523] [Example 54] Preparation of (R)-1-(4'-cyanophenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-cyanoacetophenone using a catalyst (Catalyst 17) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C2, granular)

[0524] The target (R)-1-(4'-cyanophenyl)ethanol was prepared by the same procedure as in Example 40, except that 4'-cyanoacetophenone (0.29 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 25.

[0525] GC retention time (measurement condition 3); 4'-cyanoacetophenone: 6.05 min, (R)-1-(4'-cyanophenyl)ethanol: 16.94 min, (S)-1-(4'-cyanophenyl)ethanol: 19.63 min.

[0526] [Example 55] Preparation of (R)-1-(4'-cyanophenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-cyanoacetophenone using a catalyst (Catalyst 16) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2, granular)

[0527] The target (R)-1-(4'-cyanophenyl)ethanol was prepared by the same operation as in Example 39, except that 4'-cyanoacetophenone (0.29 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 25.

[0528] [Comparative Example 14] Preparation of (R)-1-(4'-cyanophenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-cyanoacetophenone using (R,R)-Ts-DENEB complex

[0529] Table 25 shows the reaction conversion rate and optical purity calculated from the GC analysis results of the target (R)-1-(4'-cyanophenyl)ethanol prepared by the same operation as Comparative Example 2, except that 4'-cyanoacetophenone (0.29 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 5 hours.

[0530] [Comparative Example 15] Preparation of (R)-1-(4'-cyanophenyl)ethanol by non-hydrogen transfer reaction of 4'-cyanoacetophenone using (R,R)-Ts-DENEB complex in the presence of formic acid-triethylamine

[0531] The target (R)-1-(4'-cyanophenyl)ethanol was prepared by the same operation as Comparative Example 3, except that 4'-cyanoacetophenone (0.29 g, 2.0 mmol) was used as the raw material and the heating and stirring time was changed to 1 hour. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 25.

[0532] Table 25: Reaction conversion rate and optical purity calculated from GC analysis results

[0533] catalyst menstruum reducing agent Reaction time (time) Turnover rate (%) Optical purity (% ee) Example 54 Ts-DENEB / Activated Carbon C2 (Granular) Water-ethanol potassium formate 5 93.4 77.5 Example 55 Ts-DENEB / Activated Carbon A2 (Granular) Water-ethanol potassium formate 5 54.3 65.1 Comparative Example 14 Ts-DENEB Water-ethanol potassium formate 5 99.2 79.1 Comparative Example 15 Ts-DENEB doesn't exist formic acid-triethylamine 1 99.8 86.4

[0534] The effects on reaction conversion rate and optical purity in the production of (R)-1-(4'-tert-butylphenyl)ethanol by the auxiliary hydrogen transfer reaction of 4'-tert-butylacetophenone attributable to the catalyst of the present invention were examined. The results are shown in Table 26.

[0535] [Example 56] Preparation of (R)-1-(4'-tert-butylphenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-tert-butylacetophenone using a catalyst (Catalyst 17) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C2, granular)

[0536] The target (R)-1-(4'-tert-butylphenyl)ethanol was prepared by the same procedure as in Example 40, except that 4'-tert-butylacetophenone (0.35 g, 2.0 mmol) was used as the raw material, distilled water (10 mL) and ethanol (10 mL) were used as solvents, and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 26.

[0537] GC retention time (measurement condition 4); 4'-tert-butylacetophenone: 20.38 min, (R)-1-(4'-tert-butylphenyl)ethanol: 27.94 min, (S)-1-(4'-tert-butylphenyl)ethanol: 29.81 min.

[0538] [Example 57] Preparation of (R)-1-(4'-tert-butylphenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-tert-butylacetophenone using a catalyst (Catalyst 16) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2, granular)

[0539] The target (R)-1-(4'-tert-butylphenyl)ethanol was prepared by the same procedure as in Example 39, except that 4'-tert-butylacetophenone (0.35 g, 2.0 mmol) was used as the raw material, distilled water (10 mL) and ethanol (10 mL) were used as solvents, and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 26.

[0540] [Comparative Example 16] Preparation of (R)-1-(4'-tert-butylphenyl)ethanol by auxiliary hydrogen transfer reaction of 4'-tert-butylacetophenone using (R,R)-Ts-DENEB complex

[0541] The target (R)-1-(4'-tert-butylphenyl)ethanol was prepared by the same procedure as Comparative Example 2, except that 4'-tert-butylacetophenone (0.35 g, 2.0 mmol) was used as the raw material, distilled water (10 mL) and ethanol (10 mL) were used as solvents, and the heating and stirring time was changed to 5 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 26.

[0542] [Comparative Example 17] Preparation of (R)-1-(4'-tert-butylphenyl)ethanol by non-hydrogen transfer reaction of 4'-tert-butylacetophenone using (R,R)-Ts-DENEB complex in the presence of formic acid-triethylamine

[0543] The target (R)-1-(4'-tert-butylphenyl)ethanol was prepared by the same procedure as Comparative Example 3, except that 4'-tert-butylacetophenone (0.35 g, 2.0 mmol) was used as the raw material, distilled water (10 mL) and ethanol (10 mL) were used as solvents, and the heating and stirring time was changed to 3 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 26.

[0544] Table 26: Reaction conversion rate and optical purity calculated from GC analysis results

[0545] catalyst menstruum reducing agent Reaction time (time) Turnover rate (%) Optical purity (% ee) Example 56 Ts-DENEB / Activated Carbon C2 (Granular) Water-ethanol potassium formate 5 99.7 97.3 Example 57 Ts-DENEB / Activated Carbon A2 (Granular) Water-ethanol potassium formate 5 77.4 95.2 Comparative Example 16 Ts-DENEB Water-ethanol potassium formate 5 78.6 96.5 Comparative Example 17 Ts-DENEB doesn't exist formic acid-triethylamine 3 98.5 97.7

[0546] The effects on reaction conversion rate and optical purity in the production of (S)-pinacoryl alcohol by the hydrogen transfer reaction of pinacholine attributed to the catalyst of the present invention were examined. The results are shown in Table 27.

[0547] [Example 58] Preparation of (S)-pinacoryl alcohol by sub-hydrogen transfer reaction of pinacholine using a catalyst (Catalyst 17) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (C2, granular)

[0548] The target (S)-pinacoryl alcohol was prepared by the same procedure as in Example 40, except that 181.8 mg (0.02 mmol, 1.0 mol%) of catalyst was used, pinacholine (0.20 g, 2.0 mmol) was used as the raw material, and the heating and stirring time was changed to 7 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 27.

[0549] GC retention time (measurement condition 5); pinacolin: 3.12 min, (S)-pinacoryl alcohol: 9.13 min, (R)-pinacoryl alcohol: 9.69 min.

[0550] [Example 59] Preparation of (S)-pinacoryl alcohol by sub-hydrogen transfer reaction of pinacholine using a catalyst (Catalyst 16) containing a (R,R)-Ts-DENEB complex adsorbed on activated carbon (A2, granular)

[0551] The target (S)-pinacoryl alcohol was prepared by the same procedure as in Example 39, except that 194.0 mg (0.02 mmol, 1.0 mol%) of catalyst was used, pinacholine (0.20 g, 2.0 mmol) was used as the raw material, and the heating and stirring time was changed to 7 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 27.

[0552] [Comparative Example 18] Preparation of (S)-pinacoryl alcohol by sub-hydrogen transfer reaction of pinacholine using (R,R)-Ts-DENEB complex

[0553] The target (S)-pinacoryl alcohol was prepared by the same procedure as Comparative Example 2, except that 13.0 mg (0.02 mmol, 1.0 mol%) of catalyst was used, pinacholine (0.20 g, 2.0 mmol) was used as the raw material, and the heating and stirring time was changed to 7 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 27.

[0554] [Comparative Example 19] Preparation of (S)-pinacoryl alcohol by sub-hydrogen transfer reaction of pinacolin using (R,R)-Ts-DENEB complex in the presence of formic acid-triethylamine

[0555] The target (S)-pinacoryl alcohol was prepared by the same procedure as Comparative Example 3, except that 13.0 mg (0.02 mmol, 1.0 mol%) of catalyst was used, pinacholine (0.20 g, 2.0 mmol) was used as the raw material, and the heating and stirring time was changed to 7 hours. The reaction conversion rate and optical purity calculated from the GC analysis results are shown in Table 27.

[0556] Table 27: Reaction conversion rate and optical purity calculated from GC analysis results

[0557] catalyst menstruum reducing agent Reaction time (time) Turnover rate (%) Optical purity (% ee) Example 58 Ts-DENEB / Activated Carbon C2 (Granular) Water-ethanol potassium formate 7 89.5 71.0 Example 59 Ts-DENEB / Activated Carbon A2 (Granular) Water-ethanol potassium formate 7 93.8 75.1 Comparative Example 18 Ts-DENEB Water-ethanol potassium formate 7 34.7 45.6 Comparative Example 19 Ts-DENEB doesn't exist formic acid-triethylamine 7 57.0 47.3

[0558] In this way, it was found that in the production of a specific alcohol, using a complex supported on activated carbon imparts optical purity exceeding that of conventional homogeneous complexes.

[0559] <Analysis 4> In the coexistence of (R,R)-Ts-DENEB complex and π-conjugated compound 1 H NMR analysis

[0560] After adding (R,R)-Ts-DENEB (20.0 mg, 0.0308 mmol) and a predetermined amount of pyrene to an NMR sample tube, 0.7 mL of dichloroform containing 0.05% trimethylsilane was added to completely dissolve the components. Of the obtained solution 1 When comparing the H NMR as shown in Figure 3, for the solution containing pyrene, it was observed that the peak (4.5 ppm to 6.2 ppm) attributed to protons around the aromatic ring on the ruthenium phase shifted toward the high magnetic field side. From this result, it was inferred that when (R,R)-Ts-DENEB and the π-conjugated compound coexist, an interaction occurs between the aromatic ring on the ruthenium phase and the π-conjugated compound.

Claims

Claim 1 A catalyst comprising activated carbon adsorbed with a ruthenium complex represented by the following general formulas (1-1) and / or (1-2). [Chemical Formula 1] (In the above formula, solid lines represent single bonds, double lines represent double bonds, and dashed lines represent coordinate bonds; Ru represents a ruthenium atom, N represents a nitrogen atom, S represents a sulfur atom, and O represents an oxygen atom; * represents a carbon atom; j and k are integers of 0 or 1, and j+k does not equal 1, X represents a halogen, and Y represents a hydrogen atom; R 1 represents a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; an aryl group that may be substituted with an alkyl group having 1 to 10 carbon atoms; or an aralkyl group that may be substituted with an alkyl group having 1 to 10 carbon atoms; R 2 and R 3 represents a phenyl group; R 4 represents a hydrogen atom; or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms that may have substituents; R 5 to R 10 Each represents independently a hydrogen atom; or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms; R 4 and R 5 They may combine with each other to form a cross-linking site (W) represented by the following formula (W). [Chemical Formula 2] (Equation (W), n 1 The dashed line portion of the carbon chain end containing R in formulas (1-1) and (1-2) 5 Instead, it bonds to the carbon atom of the arene site, and n in formula (W) 2 The dashed line portion of the carbon chain end containing R in formulas (1-1) and (1-2) 4 Instead, bonding to the nitrogen atom of the amine site; Z represents a methylene group or oxygen atom; n 1 is an integer of 1 or 2, and;n 2 is any integer from 1 to 3.)) Claim 2 In paragraph 1, R 4 and R 5 They combine with each other to form a cross-linking site of the two groups represented by the above formula (W), where Z is an oxygen atom, and n 1 This is 1 and, n 2 A 2-person, catalyst. Claim 3 In paragraph 2, R 1 This is a 4-methylphenyl group or a methyl group, and R 2 and R 3 This is a phenyl group, and R 6 , R 7 , R 9 and R 10 This is a hydrogen atom, and R 8 This methyl group, catalyst. Claim 4 In paragraph 1, R 4 and R 5 ga does not form the two-group cross-linking sites represented by the above formula (W), and R 4 A catalyst in which hydrogen atoms are present. Claim 5 In paragraph 4, R 1 This is a 4-methylphenyl group, methyl group, isobutyl group, benzyl group, or 2',5'-dimethylbenzyl group, and R 2 and R 3 This is a phenyl group, and R 5 , R 6 , R 7 , R 8 , R 9 and R 10 This hydrogen atom, a methyl group or an isopropyl group, is a catalyst. Claim 6 A catalyst according to any one of claims 1 to 5, wherein the total mass of the ruthenium complex is 0.1 mass% or more and 25 mass% or less with respect to the total mass of the activated carbon. Claim 7 A catalyst according to any one of claims 1 to 5, wherein the specific surface area of ​​the activated carbon is 800 m² / g or more and 2000 m² / g or less. Claim 8 A method for producing a reduction product comprising a process of reducing an organic compound in the presence of a catalyst and a hydrogen donor described in claim 1. Claim 9 A method for producing an optically active alcohol, comprising a process of reducing the carbonyl group of a carbonyl compound in the presence of the catalyst and hydrogen donor described in claim 1. Claim 10 A method for producing an optically active amine, comprising a process of reducing the imino group of an imine compound in the presence of the catalyst and hydrogen donor described in claim 1. Claim 11 A method of manufacturing according to any one of claims 8 to 10, wherein the hydrogen donor is at least one selected from the group consisting of formic acid, alkali metal salt of formic acid, an alcohol having a hydrogen atom at the α-position carbon atom of a hydroxyl-substituted carbon, and hydrogen gas.

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