JP2011140469A - New ligand, transition metal complex and method for producing optically active alcohol using the complex as catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce optically active alcohols highly efficiently and highly selectively by asymmetrically reducing various ketones using as a catalyst a transition metal complex of a new triphosphane compound. <P>SOLUTION: The triphosphane compound is represented by general formula (1) (wherein R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>are each an alkyl group, aryl group, aralkyl group, cycloalkyl group, alkoxy group or the like). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel triphosphane compound, a transition metal complex having the compound as a ligand, and a catalytic reaction using the same. An effect in the catalytic reaction is an asymmetric reduction reaction of a carbonyl compound. That is, it is related with the novel manufacturing method of the optically active alcohol which uses the said phosphane compound and the periodic table group 8-10 complex which uses chiral diamine as a ligand as a catalyst.

  Transition metal complexes having chiral diphosphane compounds characterized by axial asymmetry or plane asymmetry are extremely useful as catalysts for asymmetric reactions, and many catalysts have been developed so far. Among them, a ruthenium-chiral diphosphane-chiral diamine complex in an asymmetric hydrogenation reaction of ketones has been reported to have excellent results in combination with a base compound (for example, Patent Document 1). However, in industrial implementation, there are significant problems regarding the availability of raw materials and economic efficiency in that chiral compounds are used for both diphosphane compounds and diamine compounds. On the other hand, if an achiral phosphane ligand can be used in some way instead of a chiral diphosphane compound, it can be an advantageous method for obtaining an optically active compound at a lower cost. As an example of the asymmetric hydrogenation reaction using such an achiral diphosphine ligand, there is a report using 2,2′-bis (diarylphosphino) -1,1′-biphenyl (BIPHEP) ( Non-patent document 1.). Here, an example of an asymmetric hydrogenation reaction using a ruthenium-diphosphane-optically active diamine complex is shown. However, when acetonaphthone is used as a substrate, there is a problem that optical purity is lower than BINAP, which is a typical chiral phosphane. Patent Document 2 describes an achiral benzophenone diphosphane (DPBP) ligand. That is, asymmetric reduction reaction of ketones catalyzed by ruthenium-DPBP-chiral diamine complex and rhodium-DPBP-chiral diamine complex, but raw materials that are difficult to obtain industrially are used for the production of DPBP. .

JP 11-189600 A WO2005 / 016943 A1

K. Mikami et al., Angew. Chem. Int. Ed. 1999, 38, 495.

  The object of the present invention is to use the invention of a ligand to replace an expensive chiral phosphane compound, which has a problem in industrial availability, and a chiral transition metal complex comprising the compound and a chiral diamine as a constituent component. An object is to provide a technique for producing optically active alcohols with high efficiency and high selectivity by asymmetric reduction of various ketones.

  In the course of earnest research to solve the above-mentioned problems, the inventors of the present invention have two chiralities in which an achiral triphosphane ligand having a specific structural feature and a Group 8-10 transition metal of the periodic table are ( It was found that a helical complex (L2M3 complex) having (P, M-chirality) was formed. Furthermore, it succeeded in controlling the asymmetric environment of said L2M3 complex by processing the said complex with chiral diamine. That is, an L2M3 complex composed of an achiral triphosphane ligand having C3-targetivity and a transition metal of Group 8-10 of the periodic table was synthesized, and the complex was dynamically changed in solution in the presence of the chiral diamine. And successfully obtained a complex having one chirality.

  As a result of further research, it has been found that rhodium-triphosphane-chiral diamine complexes can provide optically active alcohols by asymmetric reduction of various ketone compounds with high optical purity and high yield. It came to do.

The present invention relates to the following [1] to [8].
[1] A triphosphane compound represented by the following general formula (1).

(In General Formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different, and may have an alkyl group or a substituent which may have a substituent. Aryl group which may have a group, aralkyl group which may have a substituent, cycloalkyl group which may have a substituent, alkoxy group which may have a substituent, substituent An aryloxy group which may have a substituent, an aralkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, and an aliphatic complex which may have a substituent R ¹ and R represent a cyclic group, an aromatic heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, or a cyclic amino group which may have a substituent. ^{2, R 3} and a ^{R 4} or ^{R 5} and ^{R 6,} together with the phosphorus atom to which each is substituted It may form.)
[2] R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may have an aryl group which may have a substituent, an aliphatic heterocyclic group or a substituent which may have a substituent The triphosphane compound according to [1], which is an aromatic heterocyclic group which may have
[3] A transition metal-phosphane compound comprising the triphosphane compound according to any one of [1] or [2] above and a Group 8-10 transition metal in the periodic table.
[4] The transition metal-phosphane compound according to [3], wherein the group 8-10 transition metal in the periodic table is rhodium, palladium, ruthenium, or iridium.
[5] The transition metal-phosphane compound is represented by the following general formula (2)
[Rh ₃ (L) ₂ {N−N} ₃ ] (X) ₃ (2)
(In the formula, L represents the triphosphane compound according to claim 1 or 2, NN represents an optically active diamine, and X represents an anionic ligand.)
The optically active transition metal-phosphane compound according to [4], which is a compound represented by the formula:
[6] Catalytic organic synthesis reaction using the transition metal-phosphane compound according to any one of [3] to [5] as a catalyst.
[7] The following general formula (3)

(In the formula, R ⁷ and R ⁸ are different and each have a hydrocarbon group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or a substituent. And R ⁷ and R ⁸ may be bonded together to form a ring together with the carbon atom of the carbonyl group.)
Wherein the carbonyl compound represented by formula (4) is asymmetrically reduced using the transition metal-phosphane compound according to the above [3] or [4] as a catalyst.

(In the formula, * indicates an asymmetric carbon, and R ⁷ and R ⁸ have the same meaning as described above.)
The manufacturing method of optically active alcohol represented by these.
[8] The method for producing an optically active alcohol according to [7], wherein the optically active transition metal-phosphane compound according to [5] is used as a catalyst.

  According to the present invention, it is possible to provide a technique for producing optically active alcohols with high efficiency and high selectivity by asymmetric reduction of various ketones.

Hereinafter, the present invention will be described in detail.
The alkyl group which may have a substituent in the triphosphane compound represented by the general formula (1) may be linear or branched, for example, having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. More preferably, an alkyl group having 1 to 6 carbon atoms is used. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, tert- Examples of the alkyl group include pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cetyl group, and stearyl group.

These alkyl groups may have a substituent, and examples of the substituent include a hydrocarbon group, an aliphatic heterocyclic group, an aromatic heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group. Group, substituted amino group, cyano group, hydroxyl group, trisubstituted silyl group, halogen atom and the like.
Examples of the hydrocarbon group substituted for the alkyl group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group.

The alkyl group may be linear or branched, for example, a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cetyl group, stearyl group And alkyl groups such as
Examples of the cycloalkyl group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
The alkenyl group may be linear or branched, for example, an alkenyl group having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, specifically an ethenyl group. , Propenyl group, 1-butenyl group, pentenyl group, hexenyl group and the like.
The alkynyl group may be linear or branched, for example, an alkynyl group having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, specifically an ethynyl group. 1-propynyl group, 2-propynyl group, 1-butynyl group, 3-butynyl group, pentynyl group, hexynyl group and the like.

As an aryl group, a C6-C20 aryl group is mentioned, for example, Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group etc. are mentioned.
Examples of the aralkyl group include a group in which at least one hydrogen atom of the alkyl group is substituted with the aryl group. For example, an aralkyl group having 7 to 12 carbon atoms is preferable, specifically, a benzyl group, 2-phenyl An ethyl group, 1-phenylpropyl group, 3-naphthylpropyl group, etc. are mentioned.

  Examples of the aliphatic heterocyclic group include 2 to 14 carbon atoms and at least one hetero atom, preferably 1 to 3 hetero atoms such as a nitrogen atom, an oxygen atom, and a sulfur atom. Examples thereof include an 8-membered, preferably 5- or 6-membered monocyclic aliphatic heterocyclic group, and a polycyclic or condensed aliphatic heterocyclic group. Specific examples of the aliphatic heterocyclic group include pyrrolidyl-2-one group, piperidino group, piperazinyl group, morpholino group, tetrahydrofuryl group, tetrahydropyranyl group, tetrahydrothienyl group and the like.

  The aromatic heterocyclic group has, for example, 2 to 15 carbon atoms and contains at least one, preferably 1 to 3 hetero atoms such as nitrogen, oxygen and sulfur atoms as hetero atoms, 5 to 8 Member, preferably 5 or 6-membered monocyclic heteroaryl group, polycyclic or condensed ring heteroaryl group, specifically, furyl group, thienyl group, pyridyl group, pyrimidyl group, pyrazyl group, Pyridazyl group, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, benzofuryl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxalyl group, phthalazyl group, quinazolyl group, naphthyridyl group, cinnolyl group, benzimidazolyl group, benzoxazolyl group Group, benzothiazolyl group and the like.

  The alkoxy group may be linear or branched, for example, an alkoxy group having 1 to 6 carbon atoms, and specifically includes a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group. 2-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, 2-methylbutoxy group, 3-methylbutoxy group, 2,2-dimethylpropyloxy group, n-hexyloxy group, 2-methyl Examples include a pentyloxy group, a 3-methylpentyloxy group, a 4-methylpentyloxy group, a 5-methylpentyloxy group, a cyclohexyloxy group, a methoxymethoxy group, and a 2-ethoxyethoxy group.

Examples of the aryloxy group include an aryloxy group having 6 to 14 carbon atoms, and specific examples include a phenoxy group, a tolyloxy group, a xylyloxy group, a naphthoxy group, and an anthryloxy group.
Examples of the aralkyloxy group include an aralkyloxy group having 7 to 12 carbon atoms, and specifically include a benzyloxy group, a 4-methoxyphenylmethyl group, a 1-phenylethoxy group, a 2-phenylethoxy group, and a 1-phenyl group. Propoxy group, 2-phenylpropoxy group, 3-phenylpropoxy group, 1-phenylbutoxy group, 3-phenylbutoxy group, 4-phenylbutoxy group, 1-phenylpentyloxy group, 2-phenylpentyloxy group, 3-phenyl Pentyloxy group, 4-phenylpentyloxy group, 5-phenylpentyloxy group, 1-phenylhexyloxy group, 2-phenylhexyloxy group, 3-phenylhexyloxy group, 4-phenylhexyloxy group, 5-phenylhexyl Oxy group, 6-phenylhexyloxy group, etc. And the like.

Examples of the substituted amino group include an amino group in which one or two hydrogen atoms of the amino group are substituted with a substituent such as an alkyl group or an aryl group.
Specific examples of an amino group substituted with an alkyl group, that is, an alkyl group-substituted amino group include N-methylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, Examples thereof include mono- or dialkylamino groups such as N-cyclohexylamino group.
Specific examples of the amino group substituted with an aryl group, that is, the aryl group-substituted amino group include N-phenylamino group, N, N-diphenylamino group, N, N-ditolylamino group, N-naphthylamino group, N- Examples thereof include mono- or diarylamino groups such as naphthyl-N-phenylamino group.
Specific examples of the amino group substituted with an aralkyl group, that is, an aralkyl group-substituted amino group include mono- or diaralkylamino groups such as an N-benzylamino group and an N, N-dibenzylamino group.

Examples of the trisubstituted silyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, and a triphenylsilyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the halogenated alkyl group include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group. Can be mentioned.
Specific examples of the aryl group in the compound of the general formula (1) include the aryl groups as described above. These aryl groups may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, a trisubstituted silyl group, a halogen atom, and the like. Specific examples are as described above. Things.

  Examples of the aralkyl group in the compound of the general formula (1) include groups in which at least one hydrogen atom of the alkyl group is substituted with the aryl group. For example, an aralkyl group having 7 to 15 carbon atoms is preferable. Examples include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylpropyl group, 3-naphthylpropyl group and the like. These aralkyl groups may have a substituent, and examples of the substituent include an alkyl group and a halogen atom, and specific examples thereof include those described above.

  The cycloalkyl group in the compound of the general formula (1) is a monocyclic, polycyclic, or condensed cyclic cyclohexane having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms. An alkyl group is mentioned, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned. These cycloalkyl groups may have a substituent, and examples of the substituent include an alkyl group and a halogen atom, and specific examples thereof include those described above.

  Examples of the alkoxy group which may have a substituent in the compound of the general formula (1) include an alkoxy group and a substituted alkoxy group. The alkoxy group may be linear or branched, for example, an alkoxy group having 1 to 20 carbon atoms, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- Butoxy group, 2-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, 2-methylbutoxy group, 3-methylbutoxy group, 2,2-dimethylpropyloxy group, n-hexyloxy group, 2 -Methylpentyloxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 5-methylpentyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, methoxymethoxy group and the like. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms.

Examples of the aryloxy group which may have a substituent in the compound of the general formula (1) include an aryloxy group and a substituted aryloxy group. Examples of the aryloxy group include an aryloxy group having 6 to 20 carbon atoms, and specific examples thereof include a phenoxy group, a naphthoxy group, and an anthryloxy group. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and an aryl group as described above. The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms.
As the aralkyl group in the compound of the general formula (1), for example, an aralkyl group having 7 to 15 carbon atoms is preferable, and specifically, a benzyloxy group, a 1-phenylethyloxy group, a 2-phenylethyloxy group, a 1-phenylpropoxy group. Examples include a ruoxy group and a 3-naphthylpropyloxy group. These aralkyl groups may have a substituent, and examples of the substituent include an alkyl group and a halogen atom, and specific examples thereof include those described above.

The cycloalkyloxy group in the compound of the general formula (1) is a monocyclic, polycyclic or condensed cyclic group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms. A cycloalkyl group is mentioned, For example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned. These cycloalkyloxy groups may have a substituent, and examples of the substituent include an alkyl group and a halogen atom, and specific examples thereof include those described above.
Specific examples of the aliphatic or aromatic heterocyclic group in the compound of the general formula (1) include the heterocyclic groups described above. These heterocyclic groups may have a substituent, and examples of the substituent include an alkyl group and an aryl group, and specific examples thereof include those described above.

  Examples of the substituted amino group include amino groups in which one or two hydrogen atoms of the amino group are substituted with a substituent such as a protecting group. Specific examples of the amino protecting group include a hydrocarbon group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a substituent. The aryloxycarbonyl group which may have, the aralkyloxycarbonyl group which may have a substituent, etc. are mentioned.

Specific examples of an amino group substituted with an alkyl group, that is, an alkyl group-substituted amino group include N
Mono- or dialkylamino groups such as -methylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N-methyl-N-isopropylamino group, N-cyclohexylamino group Is mentioned.
Specific examples of the amino group substituted with an aryl group, that is, the aryl group-substituted amino group include N-phenylamino group, N, N-diphenylamino group, N-naphthylamino group, and N-naphthyl-N-phenylamino group. Mono- or diarylamino groups such as
Specific examples of an amino group substituted with an aralkyl group, that is, an aralkyl group-substituted amino group,
Examples thereof include mono- or diaralkylamino groups such as N-benzylamino group and N, N-dibenzylamino group.
Moreover, di-substituted amino groups such as N-methyl-N-phenylamino group and N-benzyl-N-methylamino group can be mentioned.
Specific examples of an amino group substituted with an acyl group, that is, an acylamino group, include formylamino group, acetylamino group, propionylamino group, pivaloylamino group, pentanoylamino group, hexanoylamino group, benzoylamino group, —NHSO _2. CH ₃ , —NHSO ₂ C ₆ H ₅ , —NHSO ₂ C ₆ H ₄ CH ₃ , —NHSO ₂ CF ₃ , —NHSO ₂ N (CH ₃ ) _{2 and the} like can be mentioned.
Specific examples of the amino group substituted with an alkoxycarbonyl group, that is, the alkoxycarbonylamino group include a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, an n-butoxycarbonylamino group, and a tert-butoxycarbonylamino group. Group, pentyloxycarbonylamino group, hexyloxycarbonylamino group and the like.
Specific examples of an amino group substituted with an aryloxycarbonyl group, that is, an aryloxycarbonylamino group include an amino group in which one hydrogen atom of the amino group is substituted with the aryloxycarbonyl group described above. Examples include a phenoxycarbonylamino group, a naphthyloxycarbonylamino group, and the like.
Specific examples of the amino group substituted with an aralkyloxycarbonyl group, that is, an aralkyloxycarbonylamino group include a benzyloxycarbonylamino group.
Examples of the ring formed with R ¹ and R ² , R ³ and R ^4, and R ⁵ and R ⁶ together with the substituted phosphorus atom include a phosphole ring, a phosphorane ring, a phosphine ring, and a phosphane ring. These rings may be substituted with an alkyl group having 1 to 4 carbon atoms.
The triphosphane compound of the present invention represented by the general formula (1) can be synthesized, for example, by the following method.

  That is, 1,3,5-tris (3′-trifluoromethanesulfonyloxyphenyl) benzene obtained by triflation of 1,3,5-tris (3′-hydroxyphenyl) benzene and diphenylphosphine oxide in the presence of a palladium catalyst. It is subjected to a coupling reaction to synthesize the corresponding phosphine oxide, and then the target C3-DPPB and C3-DM-DPPB are obtained by reducing the phosphine oxide with trichlorosilane.

Thus, the phosphane compound of this invention synthesize | combined can obtain a transition metal-phosphane complex by making it react with the transition metal compound of the 8th-10th group of a periodic table. Examples of transition metals belonging to Groups 8 to 10 of the periodic table include rhodium, ruthenium, palladium, iridium, nickel, and platinum. Among these, rhodium, ruthenium, and palladium are preferable.
Examples of the transition metal compound that can be reacted with the phosphane compound of the present invention include the following.

The ruthenium compound, for example, RuCl ₃ hydrate, RuBr ₃ hydrate, inorganic ruthenium compounds such as RuI _{3 hydrate, RuCl 2 (DMSO) 4,} [Ru (cod) Cl 2] n, [Ru ( nbd) Cl ₂ ] _n , (cod) Ru (2-methyl) ₂ , [Ru (benzone) Cl ₂ ] ₂ , [Ru (benzone) Br ₂ ] ₂ , [Ru (benzene) I ₂ ] ₂ , [Ru _{(p-cymene) Cl 2]} 2, [Ru (p-cymene) Br 2] 2, [Ru (p-cymene) I 2] 2, [Ru (mesitylene) Cl 2] 2, [Ru (mesitylene) Br _{2] 2, [Ru (mesitylene} ) I 2] 2, [Ru (hexamethylbenzene) Cl 2] _{2, [Ru (hexamethylbenzene) Br} 2] 2, [Ru (hexamethylbenzene) I 2] 2, RuCl 2 (PPh 3) 3, RuBr 2 (PPh 3) 3, RuI 2 (PPh 3) 3, RuH 4 (PPh ₃ ) ₃ , RuClH (PPh ₃ ) ₃ , RuH (OAc) (PPh ₃ ) ₃ , RuH ₂ (PPh ₃ ) _{4 and the} like. In the examples, DMSO represents dimethyl sulfoxide, cod represents 1,5-cyclooctadiene, nbd represents norbornadiene, and Ph represents a phenyl group (hereinafter the same).

Examples of rhodium compounds include [Rh (nbd) ₂ ] SbF ₆ , [Rh (cod) ₂ ] SbF ₆ , [Rh (nbd) Cl] ₂ , [Rh (cod) Cl] ₂ , [Rh (cod) ₂ ] BF ₄ , [Rh (cod) ₂ ] ClO ₄ , [Rh (cod) ₂ ] PF ₆ , [Rh (cod) ₂ ] BPh ₄ , [Rh (cod) ₂ ] BARF, [Rh (nbd) _{2 ] BF 4, [Rh (nbd} ) 2] ClO 4, [Rh (nbd) 2] PF 6, include _{[Rh (nbd) 2] BPh} 4 and the like. [Rh (nbd) ₂ ] SbF ₆ , [Rh (cod) ₂ ] SbF _{6 and the} like are preferable.

Examples of the iridium compound include [Ir (cod) (CH ₃ CN) ₂ ] BF ₄ , [Ir (cod) Cl] ₂ , [Ir (cod) ₂ ] BF ₄ , [Ir (cod) ₂ ] ClO _4. , [Ir (cod) ₂ ] PF ₆ , [Ir (cod) ₂ ] BPh ₄ , [Ir (nbd) ₂ ] BF ₄ , [Ir (nbd) ₂ ] ClO ₄ , [Ir (nbd) ₂ ] PF ₆ , [Ir (nbd) ₂ ] BPh ₄ and the like.
Examples of the palladium compound include PdCl ₂ , PdBr ₂ , Pd (OAc) ₂ , Pd (acac) ₂ , PdCl ₂ (NCMe), PdCl ₂ (NCPh), PdCl ₂ (PPh ₃ ) ₂ , PdCl ₂ (NH ₃ ) ₄ , PdCl ₂ (cod), Pd (OTf) ₂ , [PdCl (π-allyl)] _{2 and the} like. PdCl ₂ (NCMe) ₂ or the like is preferable.
Examples of the nickel compound include NiCl ₂ , NiBr _2, and NiI ₂ .

  A complex obtained by allowing a transition metal compound to act on the phosphane compound of the present invention represented by the general formula (1) can be prepared according to a previously reported method. For example, the rhodium-phosphane complex represented by the general formula (2) used in the present invention can be produced by the method described in the literature (K. Mikami et al., Chem. Commun., 2006, 2365).

Next, the manufacturing method of the optically active alcohol of this invention is demonstrated.
In the general formula (3), the hydrocarbon group which may have a substituent represented by R ⁷ and R ⁸ represents a hydrocarbon group and a substituted hydrocarbon group, and may be an aliphatic group which may have a substituent. And an aromatic heterocyclic group represents a heterocyclic group and a substituted heterocyclic group. The hydrocarbon group and the aliphatic and aromatic heterocyclic group are the same as the groups described in the general formula (1).
Examples of the substituted hydrocarbon group (hydrocarbon group having a substituent) include hydrocarbon groups in which at least one hydrogen atom of the hydrocarbon group is substituted with a substituent. Examples of the substituted hydrocarbon group include a substituted alkyl group, a substituted aryl group, a substituted alkenyl group, a substituted alkynyl group, and a substituted aralkyl group.
Examples of the substituted heterocyclic group (heterocyclic group having a substituent) include heterocyclic groups in which at least one hydrogen atom of the heterocyclic group is substituted with a substituent. Examples of the substituted heterocyclic group include a substituted aliphatic heterocyclic group and a substituted aromatic heterocyclic group.

Substituents for substituted hydrocarbon groups and substituted heterocyclic groups include hydrocarbon groups, heterocyclic groups, alkoxy groups, aryloxy groups, aralkyloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, aralkyloxycarbonyl groups, acyl groups. Acyloxy group, halogen atom, halogenated hydrocarbon group, alkylenedioxy group, amino group, substituted amino group, cyano group, nitro group, hydroxy group, substituted silyl group and the like.
The hydrocarbon group and heterocyclic group as a substituent are the same as each group demonstrated in the said General formula (1). The halogen atom, halogenated hydrocarbon group, alkoxy group, aryloxy group, aralkyloxy group and substituted amino group are the same as the groups described as substituents in the above general formula (1). The acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group and sulfonyl group are the same as the groups described as substituents of the amino group in the substituted amino group as the substituent in the general formula (1). is there.
Examples of the acyloxy group as a substituent include an acyloxy group having 2 to 18 carbon atoms derived from a carboxylic acid such as an aliphatic carboxylic acid and an aromatic carboxylic acid. Specific examples include, for example, an acetoxy group and a propionyloxy group. , Butyryloxy group, pivaloyloxy group, pentanoyloxy group, hexanoyloxy group, lauroyloxy group, stearoyloxy group, benzoyloxy group and the like.
Examples of the substituted silyl group include a tri-substituted silyl group in which three hydrogen atoms of the silyl group are substituted with a substituent such as a hydrocarbon group such as an alkyl group, an aryl group, and an aralkyl group described above. Specific examples include a trimethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, and a triphenylsilyl group.

In the general formula (3), when R ⁷ and R ⁸ are bonded to each other to form a ring together with the carbon atom of the carbonyl group, the ring may be monocyclic, polycyclic, condensed Any of a ring may be sufficient, for example, a 4-8 membered ring etc. are mentioned. Moreover, in the carbon chain which comprises a ring, you may have -O-, -NH-, etc. Specific examples of the ring in the case where R ⁷ and R ⁸ are bonded to each other to form a ring together with a carbonyl group include a cyclopentanone ring, a cyclohexanone ring, such as a 5- to 7-membered lactone ring, such as 5-7 membered lactam ring etc. are mentioned. The ring to be formed may be any ring as long as the carbon atom of the carbonyl group in the general formula (3) can become an asymmetric carbon by an asymmetric hydrogenation reaction.
The method for producing an optically active secondary alcohol of the present invention is carried out in the presence of the asymmetric synthesis catalyst according to the present invention.
As an asymmetric synthesis catalyst of the present invention, for example, a rhodium-phosphane complex can be produced by the method described in the literature (K. Mikami et al., Chem. Commun., 2006, 2365).

  Specific examples of the optically active diamine compound represented by NN used in the present invention include, for example, 1,2-diaminopropane, 2-methyl-1,3-diaminobutane, 2,3-diaminobutane, , 2-diaminopentane, 1,3-diaminopentane, 1,2-cyclopentanediamine, 1,2-cyclohexanediamine, 1,2-cycloheptanediamine, 2,3-dimethyl-2,3-diaminobutane, 2 -Dimethylamino-1-phenylethylamine, 2-diethylamino-1-phenylethylamine, 2-diisopropylamino-1-phenylethylamine, 1,2-diphenylethylenediamine, 1,2-bis (4-methoxyphenyl) ethylenediamine, 1, 2-dicyclohexylethylenediamine, 1,2-bis (4-N, N-dimethyl) Aminophenyl) ethylenediamine, 1,2-bis (4-N, N-diethylaminophenyl) ethylenediamine, 1,2-bis (4-N, N-dipropylaminophenyl) ethylenediamine, (N-benzenesulfonyl) -1, 2-bis (4-N, N-dimethylaminophenyl) ethylenediamine, (Np-toluenesulfonyl) -1,2-bis (4-N, N-dimethylaminophenyl) ethylenediamine, (N-methanesulfonyl)- 1,2-bis (4-N, N-dimethylaminophenyl) ethylenediamine, (N-trifluoromethanesulfonyl) -1,2-bis (4-N, N-dimethylaminophenyl) ethylenediamine, (N-benzenesulfonyl) -1,2-bis (4-N, N-diethylaminophenyl) ethylenediamine, N-benzenesulfonyl) -1,2-bis (4-N, N-dipropylaminophenyl) ethylenediamine, 1-methyl-2,2-diphenylethylenediamine, 1-isobutyl-2,2-diphenylethylenediamine, 1-isopropyl -2,2-diphenylethylenediamine, 1-methyl-2,2-di (p-methoxyphenyl) ethylenediamine, 1-isobutyl-2,2-di (p-methoxyphenyl) ethylenediamine, 1-isopropyl-2,2- Di (p-methoxyphenyl) ethylenediamine, 1-benzyl-2,2-di (p-methoxyphenyl) ethylenediamine, 1-methyl-2,2-dinaphthylethylenediamine, 1-isobutyl-2,2-dinaphthylethylenediamine, 1-isopropyl-2,2-dinaphthylethylenedia N, N′-bis (phenylmethyl) -1,2-diphenyl-1,2-ethylenediamine, N, N′-bis (mesitylmethyl) -1,2-diphenyl-1,2-ethylenediamine, N, N Examples include optically active substances such as' -bis (naphthylmethyl) -1,2-diphenyl-1,2-ethylenediamine.

The amount of the asymmetric synthesis catalyst used is appropriately selected from the range of usually 10 ^-1 to 10 ^-4 equivalents, preferably 10 ^-2 to 10 ^-3 equivalents, relative to the ketones.
The method for producing the optically active secondary alcohol of the present invention, that is, the asymmetric hydrogenation reaction of the ketones represented by the general formula (3) is performed by a hydrogen transfer reaction.
In the asymmetric hydrogenation reaction by hydrogen transfer reaction, it is preferable that a hydrogen donating substance is present in the reaction system. The hydrogen-donating substance is an organic compound and / or an inorganic compound, and any compound can be used as long as it can donate hydrogen in the reaction system by, for example, thermal action or catalytic action.

Examples of the hydrogen donating substance include formic acid or a salt thereof, a combination of formic acid and a base, hydroquinone, phosphorous acid, alcohols and the like. Among these, formic acid or a salt thereof, a combination of formic acid and a base, alcohols and the like are particularly preferable.
Examples of formic acid salts in formic acid or salts thereof include formic acid metal salts such as alkali metal salts and alkaline earth metal salts of formic acid, ammonium salts, and substituted amine salts.
Any formic acid salt form or substantially formic acid salt form may be used in the combined reaction system of formic acid and base.
Examples of the alkali metal that forms a salt with formic acid include lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal include magnesium, calcium, strontium, barium and the like.
Bases for forming formic acid metal salts such as alkali metal salts and alkaline earth metal salts of these formic acids, ammonium salts, substituted amine salts, etc., and bases in a combination of formic acid and bases include ammonia, inorganic bases, An organic base etc. are mentioned.

Examples of the inorganic base include potassium carbonate, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydroxide, magnesium carbonate, calcium carbonate and other alkali or alkaline earth metal salts, hydrogenated Examples thereof include metal hydrides such as sodium, sodium borohydride, lithium aluminum hydride and the like.
Examples of the organic base include alkali metal alkoxides such as potassium methoxide, sodium methoxide, lithium methoxide, sodium ethoxide, potassium isopropoxide, potassium tert-butoxide, potassium naphthalenide, sodium acetate, potassium acetate, acetic acid. Alkali / alkaline earth metal salts such as magnesium and calcium acetate, triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine, 1,5-diazabicyclo [4.3.0] nona Organic amines such as -5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, tri-n-butylamine, N-methylmorpholine, methylmagnesium bromide, ethylmagnesium bromide, odor Propyl Magnesium, methyl lithium, ethyl lithium, propyl lithium, n- butyl lithium, organic metal compounds such as tert- butyl lithium, and the like quaternary ammonium salts.

As the alcohol as a hydrogen-donating substance, lower alcohols having a hydrogen atom at the α-position are preferable. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and the like. Among them, isopropanol is preferable.
The amount of the hydrogen-donating substance used is appropriately selected from the range of usually 2 to 20 equivalents, preferably 4 to 10 equivalents, with respect to the ketones.

In addition, the method for producing an optically active secondary alcohol of the present invention may be used in combination with an organic solvent according to the type of ketones used.
Examples of the organic solvent used include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane and octane, and halogens such as dichloromethane, chloroform, carbon tetrachloride and dichloroethane. Hydrocarbons such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dimethoxyethane, tetrahydrofuran, dioxane, dioxolane and the like such as methanol, ethanol, 2-propanol, n-butanol, tert-butanol, benzyl alcohol Alcohols such as ethylene glycol, propylene glycol, 1,2-propanediol, glycerin and other polyhydric alcohols such as N, N-dimethylformamide, N, N Amides such as dimethylacetamide, acetonitrile, N- methylpyrrolidone, dimethyl sulfoxide and the like. These solvents may be used alone or in appropriate combination of two or more.
The amount of the organic solvent used is appropriately selected from the range of usually 1 to 10 times, preferably 2 to 5 times the volume of the ketone used.
The reaction temperature is appropriately selected from the range of usually 15 to 100 ° C., preferably 20 to 80 ° C. in consideration of economy and the like, and it is usually desirable to carry out at a relatively low temperature.
While the reaction time varies depending on the type and amount of the asymmetric hydrogenation catalyst used, the type and concentration of the ketone compound used, the reaction conditions such as the reaction temperature, etc., it may be about several minutes to several tens of hours, usually 4 to 48 hours Preferably, it is appropriately selected from the range of 6 to 24 hours.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples.
In addition, the apparatus used for the measurement of physical properties etc. in the following examples is as follows.
¹ H-NMR: Bruker AV300 (300 MHz)
³¹ P-NMR: Bruker AV300 (121 MHz)
Gas chromatography (hereinafter abbreviated as GC): GC-14B (Shimadzu Corporation) PEG-20 M
CP-Cyclodextrin-β-2,3,6-M-19 (id 0.25 mm x 25 m, CHROMPACK; GL Science)

  The symbols and abbreviations used in the examples are as follows.

ＤＰＥＮ（小文字も同じ）：１，２−ジフェニルエチレンジアミン

DPEN (lower case is the same): 1,2-diphenylethylenediamine

Example 1 Synthesis of 1,3,5-tris (3′-diphenylphosphinophenyl) benzene (C ₃ -DPPB) (1) 1,3,5-tris (3′-trifluoromethanesulfonyloxyphenyl) Synthesis of benzene 1.8 g (5.0 mmol) of 1,3,5-tris (3′-hydroxyphenyl) benzene and 122 mg (1.0 mmol) of dimethylaminopyridine were dissolved in 30 ml of methylene chloride under a nitrogen atmosphere. Cooled to. To this, 2.3 ml (20 mmol) of 2,6-lutidine was added, and then 3.0 ml (18 mmol) of trifluoromethanesulfonic anhydride was added dropwise, followed by stirring at room temperature for 18 hours. The reaction mixture was washed with water and brine and then dried over magnesium sulfate. After distilling off the solvent under reduced pressure, purification by silica gel column chromatography (ethyl acetate: hexane = 1: 4) gave 3.1 g (82% yield) of the title compound.

(2) Synthesis of 1,3,5-tris (3′-diphenylphosphinylphenyl) benzene 3.0 g (4.0 mmol) of 1,3,5-tris (3′-trifluoromethanesulfonyloxyphenyl) benzene, 89.8 mg (0.4 mmol) of palladium acetate, 170.6 mg (0.4 mmol) of 1,4-bis (diphenylphosphino) butane and 3.6 g (18 mmol) of diphenylphosphine oxide were dissolved in 30 ml of dimethyl sulfoxide under a nitrogen atmosphere. Further, 0.7 ml (4 mmol) of N, N-diisopropylethylamine was added and stirred at 100 ° C. for 18 hours. The reaction mixture was cooled to room temperature and 20 ml of methylene chloride was added. The solution was washed successively with 1N aqueous hydrochloric acid, water and brine, and then dried over magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (ethyl acetate → methylene chloride: methanol = 10: 1) to obtain 3.2 g (89% yield) of the title compound.

(3) Synthesis of 1,3,5-tris (3′-diphenylphosphinophenyl) benzene 3.2 g (3.5 mmol) of 1,3,5-tris (3′-diphenylphosphinylphenyl) benzene was nitrogenated. It melt | dissolved in 25 ml of toluene under atmosphere, and also the solution which added 19.4 ml (140 mmol) of triethylamine was cooled at 0 degreeC. Trichlorosilane 3.5ml (35mmol) was added there, and it stirred for 30 minutes with 0 degreeC. Then, it raised to the temperature which refluxed slowly, and was refluxed for 4 hours. The reaction mixture was cooled to 0 ° C., and 50 ml of 25% aqueous sodium hydroxide solution was slowly added dropwise. The aqueous layer was extracted with 25 ml of methylene chloride, washed twice with 1N aqueous hydrochloric acid solution, and dried over magnesium sulfate. After concentration under reduced pressure and evaporation of the solvent, purification by silica gel column chromatography (ethyl acetate: hexane = 1: 6) gave 1.1 g (35% yield) of the title compound.
³¹ P-NMR (CDCl ₃ ): δ −4.63 (s)

Example 2 Synthesis of 1,3,5-tris (3′-di- (3,5-xylyl) phosphinophenyl) benzene (C ₃ -DM-DPPB) (1) 1,3,5-Tris Synthesis of (3′-di- (3,5-xylyl) phenylphosphinylphenyl) benzene 1,3,5-tris (3′-trifluoromethanesulfonyloxyphenyl) benzene 750 mg (1 mmol), palladium acetate 22.4 mg (0.1 mmol), 42.6 mg (0.1 mmol) of 1,4-bis (diphenylphosphino) butane and 1.2 g (4.5 mmol) of di- (3,5-xylyl) phosphine oxide under a nitrogen atmosphere Dissolved in 20 ml of dimethyl sulfoxide, further added 0.2 ml (1.0 mmol) of N, N-diisopropylethylamine and stirred at 100 ° C. for 18 hours. The reaction mixture was cooled to room temperature and 20 ml of methylene chloride was added. The solution was washed successively with 1N aqueous hydrochloric acid, water and brine, and then dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography (ethyl acetate → methylene chloride: methanol = 10: 1) to obtain 838 mg (78% yield) of the title compound.

(2) Synthesis of 1,3,5-tris (3′-di- (3,5-xylyl) phosphinophenyl) benzene 1,3,5-tris (3′-di- (3,5-xylyl) A solution obtained by dissolving 752 mg (0.7 mmol) of phenylphosphinylphenyl) benzene in 15 ml of toluene under a nitrogen atmosphere and further adding 3.9 ml (28 mmol) of triethylamine was cooled to 0 ° C. Trichlorosilane 0.7ml (7.0mmol) was added there, and it stirred for 30 minutes with 0 degreeC. Then, it raised to the temperature which refluxed slowly, and was refluxed for 4 hours. The reaction mixture was cooled to 0 ° C., and 25 ml of 25% aqueous sodium hydroxide solution was slowly added dropwise. The aqueous layer was extracted with 10 ml of methylene chloride, washed twice with 1N aqueous hydrochloric acid solution, and then dried over magnesium sulfate. After concentration under reduced pressure and evaporation of the solvent, purification by silica gel column chromatography (ethyl acetate: hexane = 1: 6) gave 309 mg (43% yield) of the title compound.

Example 3 Synthesis of Pd ₃ Cl ₆ (C ₃ -dppb) ₂ PdCl ₂ (NCMe) ₂ (38.9 mg, 0.15 mmol), C ₃ -DPBP (85) in a Schlenk tube at room temperature under an argon stream. 9 mg, 0.1 mmol) and methylene chloride (10 mL) was added. After stirring for 3 hours, the reaction solution was concentrated under reduced pressure to obtain Pd ₃ Cl ₆ (C ₃ -DPPB) ₂ (106.9 mg, 95% yield).
¹ H-NMR (CDCl ₃ ): δ 6.93 (t, 6H, J = 7.8 Hz), 7.37-7.86 (m, 72H), 8.08 (s, 6H), 9.64 (T, 6H, J = 7.5 Hz)
³¹ P-NMR (CDCl ₃ ): δ 24.79 (s)

For the obtained Pd ₃ Cl ₆ (C ₃ -dppb) ₂ complex, crystal data and diffraction data were collected using a single crystal X-ray structure analyzer AFC10 / Saturn (manufactured by Rigaku Corporation) (Mo Kα (λ = The collected diffraction data revealed the structure of each single crystal (SIR92), and the crystals of the palladium-triphosphane organometallic complex (Pd ₃ C1 _6- (C ₃ -dppb) ₂ ) as a result of structural analysis, showing a C3 symmetry ligand from the crystal upper surface as shown in (Fig. 2). from the side surface orthogonal shows a C2 symmetry, a D3-point group. that _is, C 3 _-dppb2 molecule (L) It was revealed that an L2M3 organometallic complex was formed with palladium (M) and had a C3-helical conformation.

(Example 4) Synthesis of [Rh ₃ (C ₃ -dm-dppb) ₂ (nbd) ₃ ] (SbF ₆ ) ₃ [Rh (nbd) ₂ ] SbF ₆ (78 .4 mg, 0.15 mmol) and C ₃ -DM-DPPB (2) (102.7 mg, 0.1 mmol) were weighed and methylene chloride (10 mL) was added. After stirring for 3 hours, the orange residue obtained by concentrating the reaction solution under reduced pressure was washed three times with diethyl ether, and [Rh ₃ (C ₃ -dm-dppb) ₂ (nbd) ₃ ] (SbF ₆ ). ₃ (153.9 mg, 92% yield) was obtained.
¹ H-NMR (CDCl ₃ ) δ 2.26 (br, 72H), 2.36 (br, 6H), 4.13 (d, 6H, J = 19.5 Hz), 4.48-4.72 ( m, 12H), 6.78-7.81 (m, 66H).
³¹ P-NMR (CDCl ₃ ) δ 29.39 (d, J _P-Rh = 155.5 Hz).

(Example _{5) [Rh 3 (C 3} -dm-dppb) 2 (cod) 3] (SbF 6) 3 Synthesis 1,3,5-tris (3'-- (3,5-xylyl) phosphate Finophenyl) benzene (C ₃ -DM-DPPB) 10.3 mg (0.010 mmol), [Rh (cod) ₂ ] SbF ₆ 8.3 mg (0.015 mmol) were dissolved in 5 ml of methylene chloride under a nitrogen atmosphere. Stir at room temperature for 2 hours. After the solvent was distilled off under reduced pressure, the reaction mixture was washed 3 times with 3 ml of diethyl ether. After washing, drying under reduced pressure gave 16.1 mg (95% yield) of the title compound.

Example 6 Synthesis of [Rh ₃ (C ₃ -dm-dppb) ₂ (acetone) ₃ ] (SbF ₆ ) ₃ [Rh ₃ (C ₃ -dm-dppb) was added to a Schlenk tube at room temperature under an argon stream. ₂ (nbd) ₃ ] (SbF ₆ ) ₃ (33.5 mg, 0.01 mmol) was weighed and acetone (5 mL) was added. After the mixture was frozen, hydrogen gas (ab.1 atm) was charged using a balloon filled with hydrogen gas. After warming to room temperature and stirring for 30 minutes, the orange residue obtained by concentrating the reaction solution under reduced pressure was washed three times with diethyl ether, and [Rh ₃ (C ₃ -dm-dppb) ₂ (acetone) ₃ ] (SbF ₆ ) ₃ (23.9 mg, quantitative yield) was obtained.

(Example 7) Synthesis of [Rh ₃ (C ₃ -dm-dppb) ₂ {(S, S) -dpen} ₃ ] (SbF ₆ ) ₃ [Rh ₃ (C _3- dm-dppb) ₂ (acetone) ₃ ] (SbF ₆ ) ₃ (23.9 mg, 0.01 mmol) and (S, S) -DPEN (6.3 mg, 0.03 mmol) were weighed and chloroform (5 mL ) Was added. After the mixture was stirred at room temperature for 5 minutes, the reaction solution was concentrated under reduced pressure to obtain [Rh ₃ (C ₃ -dm-dppb) ₂ {(S, S) -dpen} ₃ ] (SbF ₆ ) ₃ (41. 2 mg, quantitative yield).
¹ H-NMR (CDCl ₃ ) δ 2.32 (br, 72H), 4.18 (d, 6H, J = 7.8 Hz), 4.86 (d, 6H, J = 7.8 Hz), 4. 99 (s, 6H), 6.92-7.67 (m, 96H).
³¹ P-NMR (CDCl ₃ ) δ 49.80 (d, J _P-Rh = 132.4 Hz).

Example 8 Synthesis of (R) -1- (1-Naphthyl) ethanol [Rh ₃ (C ₃ -dm-dppb) ₂ {(S, S) -dpen} ₃ ] (in a Schlenk tube under an argon stream) SbF ₆ ) ₃ (12.4 mg, 0.003 mmol) was weighed, 2-propanol (3.6 mL) was added, and the mixture was stirred at room temperature. To this solution, t-BuOK / 2-propanol (0.1 M, 0.6 mL, 0.06 mmol) was added and stirred at room temperature for 20 minutes, then 1-acetonathone (38 μL, 0.33 mmol) was added, and 24 hours at room temperature. Stir for hours. The residue obtained by concentrating the reaction solution under reduced pressure was subjected to silica gel column chromatography (hexane / EtOAc = 3/1) to give (R) -1- (1-Naphthyl) ethanol (43.7 mg, 77% yield). Rate, 82% ee).

(Comparative Example) Synthesis of (R) -1- (1-Naphthyl) ethanol The rhodium complex of Example 8 was converted to [Rh ₃ (C ₃ -dm-dppb) ₂ {(S, S) -dpen} ₃ ] ( SbF ₆ ) ₃ to [Rh {(R) -binap} {(S, S) -dpen}] (SbF ₆ ), except that the reaction was further carried out at 60 ° C., the same operation as in Example 8 was performed. As a result, the target product (R) -1- (1-Naphthyl) ethanol was obtained with a yield of 98% and an optical purity of 72% ee. The optical purity of the target product was lower than when the compound of the present invention was used.

  The optically active transition metal-phosphane complex of the present invention is useful as a catalyst for various organic synthesis reactions, particularly hydrogen transfer-type asymmetric reduction reaction, etc., and production of optically active secondary alcohols useful as pharmaceutical intermediates and liquid crystal materials It can be used effectively.

1 shows a ¹ H-NMR chart of 1,3,5-tris (3′-diphenylphosphinophenyl) benzene (C ₃ -DPPB) obtained in Example 1. FIG. It shows a _{Pd 3 Cl 6 (C 3 -dpppb} ) 2 single crystal X-ray structural analysis results.

Claims (8)

The following general formula (1)

(In General Formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different, and may have an alkyl group or a substituent which may have a substituent. Aryl group which may have a group, aralkyl group which may have a substituent, cycloalkyl group which may have a substituent, alkoxy group which may have a substituent, substituent An aryloxy group which may have a substituent, an aralkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, and an aliphatic complex which may have a substituent R ¹ and R represent a cyclic group, an aromatic heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, or a cyclic amino group which may have a substituent. ^{2, R 3} and a ^{R 4} or ^{R 5} and ^{R 6,} together with the phosphorus atom to which each is substituted It may form.)
A triphosphane compound represented by: R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have an aryl group which may have a substituent, an aliphatic heterocyclic group which may have a substituent or a substituent. The triphosphane compound according to claim 1, which may be an aromatic heterocyclic group. A transition metal-phosphane compound comprising the triphosphane compound according to claim 1 or 2 and a Group 8-10 transition metal of the periodic table. The transition metal-phosphane compound according to claim 3, wherein the group 8-10 transition metal of the periodic table is rhodium, palladium, ruthenium or iridium. The transition metal-phosphane compound is represented by the following general formula (2)
[Rh ₃ (L) ₂ {N−N} ₃ ] (X) ₃ (2)
(In the formula, L represents the triphosphane compound according to claim 1 or 2, NN represents an optically active diamine, and X represents an anionic ligand.)
The optically active transition metal-phosphane compound according to claim 4, which is a compound represented by the formula: Catalytic organic synthesis reaction using the transition metal-phosphane compound according to any one of claims 3 to 5 as a catalyst. The following general formula (3)

(In the formula, R ⁷ and R ⁸ are different and each have a hydrocarbon group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or a substituent. R ⁷ and R ⁸ may be bonded together to form a ring together with the carbon atom of the carbonyl group.
Wherein the carbonyl compound represented by formula (4) is asymmetrically reduced using the transition metal-phosphane compound according to claim 3 or 4 as a catalyst.

(In the formula, * indicates an asymmetric carbon, and R ⁷ and R ⁸ have the same meaning as described above.)
The manufacturing method of optically active alcohol represented by these. The method for producing an optically active alcohol according to claim 7, wherein the optically active transition metal-phosphane compound according to claim 5 is used as a catalyst.

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