JP4718786B2 - Method for producing optically active alcohol having nitrogen-containing heterocycle - Google Patents

Description

  The present invention relates to optically active alcohols having nitrogen-containing heterocycles, which are useful as synthetic intermediates for physiologically active substances, pharmaceuticals, agricultural chemicals, and catalysts for asymmetric synthesis from ketone compounds having nitrogen-containing heteroaromatic salts. The present invention relates to a method for producing with high reaction yield and high optical purity.

An optically active alcohol having a nitrogen-containing heterocycle (an optically active alcohol having a piperidine or tetrahydropyridyl ring) is an important compound as a synthetic intermediate for pharmaceuticals, agricultural chemicals, catalysts for asymmetric synthesis, and the like. For example, E2001, SUN- N5030 and ifenpulsyl hydrochloride are known. As a conventionally known method for producing an optically active alcohol having a nitrogen-containing heterocycle,
1) There is a method of synthesizing an alcohol in which a nitrogen-containing heteroaromatic ring is partially reduced by reducing a ketone compound having a nitrogen-containing heteroaromatic salt with sodium borohydride (for example, Patent Document 1). However, the alcohol to be synthesized is a racemate, and in order to obtain an optically active alcohol, it is necessary to resolve the obtained racemate by a physical or chemical method.
2) There is also a method of synthesizing optically active alcohols having nitrogen-containing heteroaromatic rings by asymmetric hydrogenation or asymmetric reduction of ketones having nitrogen-containing heteroaromatic rings using a molecular asymmetric catalyst. (For example, Non-Patent Documents 1 and 2). However, in order to synthesize an optically active alcohol having a nitrogen-containing heterocycle in which the nitrogen-containing heteroaromatic ring is partially or completely reduced, it is necessary to reduce the nitrogen-containing heteroaromatic ring separately. There were problems in terms of complexity and the yield of the target product.
Thus, there has not yet been found a method for easily reducing alcohol of high optical purity by simultaneously reducing a carbonyl group and a nitrogen-containing heteroaromatic ring from a ketone compound having a nitrogen-containing heteroaromatic salt. The development of was strongly desired.

Japanese Patent No. 3114996 Ohkuma, T .; Ishii, D .; Takeno, H .; Noyori, R. J. Am. Chem. Soc. 2000, 122, p6510. Ohkuma, T .; Koizumi, M .; Yoshida, M .; Noyori, R. Org. Lett. 2000, 2, p1749.

  The present invention has been made in view of the situation as described above. Reduction of a nitrogen-containing heteroaromatic ring and a carbonyl group in a ketone compound having a nitrogen-containing heteroaromatic salt can be carried out in one pot using a single catalyst. And providing a method for efficiently producing an optically active alcohol having a nitrogen-containing heterocycle. That is, a method for efficiently producing an optically active alcohol having a nitrogen-containing heterocycle from a ketone compound having a nitrogen-containing heteroaromatic salt by an asymmetric metal complex in the presence of a hydrogen-donating organic or inorganic compound is provided. To do.

（式中、Ｒ^１およびＲ^２は、置換基を有していても良い芳香族単環もしくは芳香族多環式炭化水素基、置換基を有していても良い飽和もしくは不飽和の脂肪族炭化水素基または脂環式炭化水素基、または、置換基を有していても良い複素単環もしくは複素多環式基であり、Ｒ^２は、さらに、独立して水素原子、ハロゲン原子、カルボキシル基、アミノ基、アミド基、水酸基、アルコキシ基またはアリロキシ基であり、または、ｎが２以上である場合には互いに結合してテトラエチレン基または１，３−ブテニル基を形成していても良く、Ｘ⁻は、ハロゲンアニオン、ボラートアニオン、ホスフェートアニオン、スルホネートアニオンまたはカルボキシレートアニオンであり、ｍは０〜５を、ｎは０〜５を示す。）で表される含窒素ヘテロ芳香族の塩をもつケトン化合物に、一般式（Ｂ）

（式中、Ｒ³およびＲ⁴は、それぞれ独立して、置換基を有していても良い芳香族単環もしくは芳香族多環式炭化水素基、置換基を有していてもよい飽和もしくは不飽和の脂肪族炭化水素基または脂環式炭化水素基、または、置換基を有してもよい複素単環または複素多環式基を示し、Ｒ³およびＲ⁴は、互いに結合して環を形成してもよく、Ｒ^５は水素原子または置換基を有していても良いアルキル基を示し、Ｒ^６は置換基を有していても良いアルキル基、置換基を有していても良い芳香族単環もしくは芳香族多環式炭化水素基、飽和もしくは不飽和の脂肪族炭化水素基または脂環式炭化水素基を示し、＊は不斉炭素原子を示す。）で表される光学活性含窒素化合物および周期表第ＶＩＩＩ族金属化合物を作用させることにより得られる不斉金属錯体ならびに水素供与体を反応させてなる、一般式（Ｃ）および／または一般式（Ｄ）

（式中、Ｒ^１、Ｒ^２、ｍ、ｎは、前記と同一である。）
で表される含窒素ヘテロ環をもつ光学活性アルコールの製造方法に関する。 As a result of intensive studies to solve the above problems, the present inventors have found that a ketone compound having a nitrogen-containing heteroaromatic salt is reacted with an optically active nitrogen-containing compound and a Group VIII metal compound of the periodic table. A high optical purity optically active alcohol having a nitrogen-containing heterocycle in which a nitrogen-containing heteroaromatic ring is partially or completely reduced by a hydrogen transfer-type asymmetric reduction reaction using a homogeneous metal complex and a hydrogen donor. The inventors have found that it can be obtained in a high yield, and have completed the present invention.
That is, the present invention relates to the general formula (A)

(In the formula, R ¹ and R ² are an aromatic monocyclic or aromatic polycyclic hydrocarbon group which may have a substituent, and a saturated or unsaturated aliphatic which may have a substituent. A hydrocarbon group, an alicyclic hydrocarbon group, or a heteromonocyclic or heteropolycyclic group which may have a substituent, and R ² is independently a hydrogen atom, a halogen atom, a carboxyl group Group, amino group, amide group, hydroxyl group, alkoxy group or allyloxy group, or when n is 2 or more, they may be bonded to each other to form a tetraethylene group or a 1,3-butenyl group. , X ⁻ represents a halogen anion, a borate anion, a phosphate anion, a sulfonate anion or a carboxylate anion, m represents 0 to 5 and n represents 0 to 5). To a ketone compound having an aromatic salt, a general formula (B)

(Wherein R ³ and R ⁴ are each independently an aromatic monocyclic or aromatic polycyclic hydrocarbon group which may have a substituent, saturated or optionally having a substituent, or An unsaturated aliphatic hydrocarbon group or an alicyclic hydrocarbon group, or a heteromonocyclic or heteropolycyclic group which may have a substituent, wherein R ³ and R ⁴ are bonded to each other to form a ring; R ⁵ represents a hydrogen atom or an alkyl group which may have a substituent, and R ⁶ may have an alkyl group or a substituent which may have a substituent. A good aromatic monocyclic or aromatic polycyclic hydrocarbon group, a saturated or unsaturated aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and * represents an asymmetric carbon atom). Asymmetry obtained by reacting an active nitrogen-containing compound and a Group VIII metal compound of the periodic table General formula (C) and / or general formula (D) obtained by reacting a metal complex and a hydrogen donor

(In the formula, R ¹ , R ² , m and n are the same as described above.)
The manufacturing method of the optically active alcohol which has a nitrogen-containing heterocycle represented by these.

The present invention also relates to a method for producing an optically active alcohol having a nitrogen-containing heterocycle, wherein m and n are 1 and R ² is substituted at the 4-position of the nitrogen-containing heterocycle.
Furthermore, the present invention provides an optically active alcohol having the nitrogen-containing heterocycle, wherein R ¹ is a phenyl group which may have a substituent and R ² is a dihydropyridazyl group which may have a substituent. Regarding the method.
The present invention also relates to a method for producing an optically active alcohol having the nitrogen-containing heterocycle, wherein R ¹ is a 4-cyanophenyl group and R ² is a 4-oxodihydropyridazyl group.

Ｒ^４が

Ｒ^６が

（式中、Ｒ^７、Ｒ^８およびＲ^９は、それぞれ独立して、水素原子、炭素数１〜８のアルキル基、ハロゲン原子、炭素数１〜８のアルコキシ基を示し、o、p、qはそれぞれ独立して１〜５を示す。）で表される構造である、前記含窒素へテロ環をもつ光学活性アルコールの製造方法に関する。
また本発明は、一般式（Ｂ）で表される光学活性含窒素化合物において、Ｒ^３およびＲ^４が互いに結合して、

（式中、Ｒ^８、pは前記と同一である。）で表される構造である、前記含窒素へテロ環をもつ光学活性アルコールの製造方法に関する。
さらに本発明は、周期表第ＶＩＩＩ族金属化合物がルテニウム化合物である、前記含窒素ヘテロ環をもつ光学活性アルコールの製造方法に関する。 Furthermore, the present invention provides an optically active nitrogen-containing compound represented by the general formula (B), wherein R ³ is

R ⁴ is

R ⁶ is

(Wherein R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom or an alkoxy group having 1 to 8 carbon atoms; o, p, q; Each independently represents 1 to 5), and relates to a method for producing an optically active alcohol having a nitrogen-containing heterocycle.
In the optically active nitrogen-containing compound represented by the general formula (B), R ³ and R ⁴ are bonded to each other.

(Wherein R ⁸ and p are as defined above), and relates to a method for producing an optically active alcohol having the nitrogen-containing heterocycle.
Furthermore, this invention relates to the manufacturing method of the optically active alcohol which has the said nitrogen-containing heterocycle whose periodic table group VIII metal compound is a ruthenium compound.

The present invention also relates to a method for producing an optically active alcohol having a nitrogen-containing heterocycle, wherein the hydrogen donor is formic acid, formate, or an alcohol compound.
Furthermore, the present invention is a method for producing an optically active alcohol having a nitrogen-containing heterocycle, and further includes one or more selected from the group consisting of organic amines, alkali metal hydroxides and alkali metal alkoxides. The said manufacturing method using a base is related.

It has never been known before that the heteroaromatic ring is reduced by a hydrogen transfer-type asymmetric reduction reaction using an asymmetric metal complex and a hydrogen donor, and the present invention has realized this for the first time. Is. In addition, the present invention uses the hydrogen transfer asymmetric reduction reaction to reduce the heteroaromatic ring and the carbonyl group at the same time, and obtains an optically active alcohol with very high stereoselectivity. It has a surprising effect.
Therefore, according to the production method of the present invention, the carbonyl group of the ketone compound having a nitrogen-containing heteroaromatic salt is reduced in one pot, and the nitrogen-containing heteroaromatic ring is also reduced, resulting in high yield and high optical purity. Thus, an optically active alcohol having a nitrogen-containing heterocycle can be easily provided. The present invention greatly contributes to related industries such as pharmaceutical intermediates of pharmaceuticals, particularly β-adrenergic effect blockers, and agricultural chemicals.

Hereinafter, the present invention will be described in detail.

According to the method for producing an optically active alcohol having a nitrogen-containing heterocycle of the present invention (general formulas (C) and (D)), the compound represented by the general formula (A) is represented by the general formula (B) according to the above reaction formula. An asymmetric metal complex obtained by reacting the optically active nitrogen-containing compound represented by the formula (III) and a metal compound of Group VIII of the periodic table and a hydrogen donor in the presence or absence of a base. Is done. At that time, the periodic table group VIII metal compound and the optically active nitrogen-containing compound may be allowed to coexist in the reaction vessel, or both are reacted before the asymmetric reduction reaction to prepare an asymmetric metal complex separately. This may be used. In order to obtain the target product with good yield, it is preferable to prepare and react such a complex in advance.
In addition, the compound represented by general formula (A) used as a raw material can be obtained by a known method, for example, by reacting a haloketone compound and a pyridine derivative in a predetermined solvent.

で表される含窒素へテロ芳香族の塩をもつケトン化合物である。 Next, the general formula (A), optically active nitrogen-containing compound (B), periodic table group VIII metal compound, hydrogen donor, base and products represented by the general formulas (C) and (D) used as raw materials The preferable aspect of is shown.
The compound used as a raw material of the present invention has the general formula (A)

A ketone compound having a nitrogen-containing heteroaromatic salt represented by the formula:

Here, in the general formula (A), R ¹ and R ² may have an aromatic monocyclic or aromatic polycyclic hydrocarbon group or substituent which may have a substituent. A saturated or unsaturated aliphatic hydrocarbon group or alicyclic hydrocarbon group, or a heteromonocyclic or heteropolycyclic group which may have a substituent, and R ² is independently A hydrogen atom, a halogen atom, a carboxyl group, an amino group, an amide group, a hydroxyl group, an alkoxy group or an allyloxy group, or when n is 2 or more, bonded to each other to form a tetraethylene group or a 1,3-butenyl group may form a, X ^- is a halogen anion, borate anion, phosphate anion, a sulfonate anion or a carboxylate anion, m is 0-5, n represents 0-5.

A substituted phenyl group is mentioned as an aromatic monocyclic hydrocarbon group which may have a substituent. Specifically, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2-methoxyphenyl, 2-chlorophenyl, 2-vinylphenyl, 3-methylphenyl, 3- Ethylphenyl, 3-isopropylphenyl, 3-methoxyphenyl, 3-chlorophenyl, 3-vinylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-vinylphenyl, 4 -Methoxyphenyl, 3,5-dimethylphenyl, cumenyl, mesityl, xylyl, 2-cyanophenyl, 4-cyanophenyl and the like. A preferred substituent exhibiting the effects of the present invention is when R ¹ is 4-cyanophenyl.

Specific examples of the aromatic polycyclic hydrocarbon group which may have a substituent include 1-naphthyl, 2-naphthyl, anthryl, phenanthryl, and indenyl groups.
The saturated or unsaturated aliphatic hydrocarbon group which may have a substituent is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an alkynyl group.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. Specifically, methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, Examples include hexyl, heptyl, octyl, nonyl, decyl, dodecyl groups and the like. A preferable substituent exhibiting the effect of the present invention is a case where R ² is methyl.

The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms. Specifically, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 1-isopropenyl, 2-butenyl, 3-butenyl, 1,3 -Butadiniel, 1-pentenyl, 2-pentenyl, 3-pentenyl group and the like are exemplified.
The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, and specific examples include acetylenyl, methylacetylenyl, phenylacetylenyl groups and the like.

The saturated or unsaturated alicyclic hydrocarbon group which may have a substituent represents a cycloalkyl group having 3 to 8 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl groups and the like, which are cycloalkyl groups having 3 to 6 carbon atoms.
Specific examples of the heteromonocyclic group which may have a substituent include thienyl, furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, triazolyl, thiazolyl, isothiazolyl, pyridyl, pyridazyl, pyridinyl, dihydropyri Examples include dazyl and 4-oxodihydropyridazyl. A preferable substituent exhibiting the effect of the present invention is a case where R ² is dihydropyridyl or 4-oxodihydropyridyl.
Specific examples of the heteropolycyclic group which may have a substituent include benzimidazolyl, benzpyrazolyl, benzothiazolyl, quinolyl, acridyl, indolyl, and phenanthridyl groups.

  Such aromatic monocyclic hydrocarbon groups, aromatic polycyclic hydrocarbon groups, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, heteromonocyclic groups and heteropolycyclic groups are further described below. May have various substituents. Specifically, halogen atoms such as fluorine, chlorine, bromine and iodine, halogen atom-containing hydrocarbon groups such as trifluoromethyl group, oxygen atom-containing substituents such as oxo, hydroxyl, alkoxy, acyl, alkoxycarbonyl, carboxyl group, Nitrogen-containing substituents such as amino, alkylamino, nitro, cyano, and azido groups, silicon-containing substituents such as trimethylsilyl and hydrosilyl groups, sulfur-containing substituents such as mercapto and alkylthio groups, phosphoryl, and triphenylphosphinyl groups Examples thereof include phosphorus atom-containing substituents such as iron-containing substituents such as ferrocenyl group.

In addition, when n is 2 or more, R ² which may be bonded to each other to form a tetraethylene group or a 1,3-butenyl group specifically includes the compound shown in FIG. .
The halogen atom of R ² is Cl, F, Br, or I, and the alkoxy group means an alkoxy group having 1 to 20 carbon atoms, specifically, a methoxy group, an ethoxy group, a propoxy group, or the like.
X ⁻ represents a halogen anion such as F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ , a borate anion such as BH ₄ ⁻ , BF ₄ ⁻ and BPh ₄ ⁻ , a phosphate anion such as PF ₆ ⁻ , CH ₃ SO ₃ ⁻ and _{p-CH 3 C 6 H 4} SO 3, sulfonate anions, such _as, CH 3 COO ^- and PhCOO ^- like carboxylate anion such. Preferred is a halogen anion, and most preferred is Br ⁻ .
Moreover, m represents 0-5, Preferably it is 0-2. n represents 0 to 5, preferably 0 to 2.

The compounds represented by the general formula (A) are more specifically shown in FIG. 1 to FIG. The ketone compound having the nitrogen-containing heteroaromatic salt of the general formula (A) is not limited to the compounds shown in FIGS. A compound in which R ¹ is an aromatic monocyclic hydrocarbon group which may have a substituent is specifically shown in FIG.

Preferred general formula (A) in the present invention is the structure of 1, 6, 7 and 8 in FIG. 1, and most preferred are 1 and 8 in FIG. In FIG -1, X ^- is the same as above, R represents a hydrogen atom, a methyl group, tetrahydropyranyl group, an allyl group, an isopropyl group, tert- butyl group, a trimethylsilyl group, tert- butyldimethylsilyl Group etc. are shown.

Further, a compound in which R ¹ in the general formula (A) is a heteromonocyclic group is more specifically shown in FIG. Further, in FIG. 2, X ⁻ is synonymous with FIG.

Furthermore, when n of R ^{2 in} the general formula (A) is 2 or more, a compound that may be bonded to each other to form a tetraethylene group or a 1,3-butenyl group is more specifically shown in FIG. Show. In FIG. 3, X ⁻ has the same meaning as in FIG.

The optically active nitrogen-containing compound constituting the asymmetric metal complex that is a catalyst used in the present invention is a diamine derivative represented by the general formula (B).

In the general formula (B), R ³ and R ⁴ may each independently have an aromatic monocyclic or aromatic polycyclic hydrocarbon group or substituent which may have a substituent. Represents a good saturated or unsaturated aliphatic hydrocarbon group or alicyclic hydrocarbon group, or a heterocyclic monocyclic or heterocyclic polycyclic group which may have a substituent, and R ³ and R ⁴ are bonded to each other And R ⁵ represents a hydrogen atom or an alkyl group which may have a substituent, and R ⁶ has an alkyl group or a substituent which may have a substituent. An aromatic monocyclic or aromatic polycyclic hydrocarbon group, a saturated or unsaturated aliphatic hydrocarbon group or an alicyclic hydrocarbon group which may be optionally present, and * represents an asymmetric carbon atom.

An aromatic monocyclic hydrocarbon group, an aromatic polycyclic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, which may have a substituent of R ³ , R ⁴ and R ⁶ ; A heteromonocyclic group and a heteropolycyclic group are synonymous with R ¹ and R ² .
The alkyl group which may have a substituent of R ⁵ and R ⁶ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specifically, linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, trifluoromethyl groups, etc. Is mentioned.
Examples of the aromatic monocyclic or aromatic polycyclic hydrocarbon group which may have a substituent for R ⁶ include a phenyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group, 1 -A naphthyl group, 2-naphthyl group, anthryl group is mentioned.

であり、Ｒ⁴が

であるか、または、
Ｒ³およびＲ⁴が互いに結合して

（式中、Ｒ^８およびＲ^９は、それぞれ独立して、水素原子、メチルおよびエチルなどの炭素数１〜８のアルキル基、Ｆなどのハロゲン原子、炭素数１〜８のアルコキシ基を示し、p、qはそれぞれ独立して１〜５を示す。）である。
また、本発明の効果を奏するのに好ましいＲ^６は、

（式中、Ｒ^７は、水素原子、メチルおよびエチルなどの炭素数１〜８のアルキル基、Ｆなどのハロゲン原子、炭素数１〜８のアルコキシ基を示し、ｏは１〜５を示す。）である。 Preferred R ³ and R ⁴ to the effect of the present invention, R ³ is

And R ⁴ is

Or
R ³ and R ⁴ are bonded together

(Wherein R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms such as methyl and ethyl, a halogen atom such as F, or an alkoxy group having 1 to 8 carbon atoms, p and q each independently represent 1 to 5).
In addition, R ^{6 that} is preferable for achieving the effects of the present invention is:

(Wherein, ^{R 7} is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 8 carbon atoms such as an alkyl group, F 1 to 8 carbon atoms such as methyl and ethyl, o is showing a 1-5. ).

  More specifically, the optically active nitrogen-containing compound represented by the general formula (B) in combination with the above-described preferred embodiments of substituents is shown more specifically. For example, N-tosyl-1,2-diphenylethylenediamine, N-mesyl -1,2-diphenylethylenediamine, N-methanesulfonyl-1,2-diphenylethylenediamine, N-methyl-N'-tosyl-1,2-diphenylethylenediamine, Np-methoxyphenylsulfonyl-1,2-diphenylethylenediamine Np-chlorophenylsulfonyl-1,2-diphenylethylenediamine, Np-mesitylsulfonyl-1,2-diphenylethylenediamine, N- (2,4,6-triisopropyl) phenylsulfonyl-1,2-diphenyl Ethylenediamine, N-trifluoromethanesulfonyl- , 2-cyclohexanediamine, N- (p-toluenesulfonyl) -1,2-cyclohexanediamine, N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine, N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine, N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine, N- (2-naphthylsulfonyl) -1,2-diphenyl Ethylenediamine, N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine, N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine, N- (4-isopropylenebenzenesulfonyl) -1,2- Diphenylethylene di Min, N-(4-ethylbenzene) -1,2-diphenyl ethylenediamine, and the like. Preferably, N-tosyl-1,2-diphenylethylenediamine, N-methanesulfonyl-1,2-diphenylethylenediamine, N- (p-toluenesulfonyl) -1,2-cyclohexanediamine, N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine, N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine, N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine, N- (1-naphthylsulfonyl) -1 , 2-Diphenylethylenediamine, N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine, N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine, N- (4-biphenylsulfonyl) -1, 2-diphenyl ethyl Diamine, N- (4-isopropylenebenzenesulfonyl) -1,2-diphenylethylenediamine, and N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine.

  The amount of the ketone compound having a nitrogen-containing heteroaromatic salt to be used (general formula A) is usually 10 by molar ratio of the ketone compound having a nitrogen-containing heteroaromatic salt to the optically active nitrogen-containing compound (general formula B). ˜100,000 is used, preferably 100 to 2,000, and most preferably 100 to 500.

The Group VIII metal compound of the periodic table of the present invention is used in combination with an optically active nitrogen-containing compound, and as its metal species, ruthenium, rhodium, iridium, cobalt, iron, nickel, palladium, platinum, osmium Examples thereof include ruthenium, rhodium and iridium. Specific compounds include RuCl ₃ -3H ₂ O, [RuCl ₂ (p-cymene)] ₂ , [RuCl ₂ (benzene)] ₂ , [RuCl ₂ (1,4-dimethylbenzene)], [RuCl ₂ ( 1,2-dimethylbenzene)], [RuCl ₂ (1,3-dimethylbenzene)], [RuCl ₂ (1,2,3-trimethylbenzene)], [RuCl ₂ (1,2,4-trimethylbenzene)], [RuCl ₂ (1,3,5-triethylbenzene)], [RuCl ₂ (mesitylene)] ₂ , [RuCl ₂ (1,2,4,5-tetramethylbenzene)] ₂ , [RuCl ₂ (1,2,3,5- tetramethylbenzene)] ₂ , [RuCl ₂ (1,2,3,4-tetramethylbenzene)] ₂ , [RuCl ₂ (pentamethylbenzene)] ₂ , [RuCl ₂ (hexamethylbenzene)] ₂ , RuCl ₂ (PPh ₃ ) ₃ , [RuCl ₂ (cod)] n, [RuCl ₂ (CO) ₃ ] ₂ , [Rh (cod) Cl] ₂ , [Cp ^* RhCl ₂ ] ₂ , [Ir (cod) Cl] ₂ , [Cp ^* IrCl ₂ ] ₂ , CoCl ₂ , NiCl ₂ , NiBr ₂ , NiCl ₂ (PPh ₃ ) ₂ , NiBr ₂ (PPh ₃ ) ₂ , PdCl ₂ , Pd (PPh ₃ ) ₄ , PdCl ₂ (CH ₃ CN) ₂ , PdCl ₂ (PhCN) ₂ , PtCl ₂ (cod), Pt (PPh ₃ ) ₄ , RuH ₂ (PPh ₃ ) ₄ , RuH ₂ (dppe) ₂ , RuH ₄ (PPh ₃ ) ₃ , Ru (cod) (cot), Ru (cod) (bezene) and the like are exemplified, preferably [RuCl ₂ (p-cymene)] ₂ , [RuCl ₂ (mesitylene)] ₂ , [RuCl ₂ (1,4-dimethylbenzene)], [RuCl ₂ (1,3,5-triethylbenzene)], [RuCl ₂ (1,2,4,5-tetramethylbenzene)] ₂ . In the above compounds, Ph represents a phenyl group, cod represents cyclooctadiene, Cp ^* represents a pentamethylcyclopentadienyl group, cot represents cyclooctatetraene, and dppe represents diphenylphosphinoethane. Cl in these compounds may be another halogen atom such as Br or I.
The mixing ratio of the periodic table group VIII metal compound and the optically active nitrogen-containing compound is between 1.0: 0.1 to 1.0: 10.0 molar ratio, preferably the periodic table VIII. It is appropriate to equimolarly mix the group metal compound and the optically active nitrogen-containing compound.

  In the production method of the present invention, the compound represented by the general formula (A), the optically active nitrogen-containing compound represented by the general formula (B), and the group VIII metal compound of the periodic table in the presence or absence of a base, The target product can be obtained by reacting in the same system, but the group VIII metal atom is reacted in advance in the presence or absence of a base group VIII metal compound and optically active nitrogen-containing compound in the periodic table. Alternatively, an asymmetric metal complex in which an optically active nitrogen-containing compound is coordinated may be separately prepared and used. When the asymmetric metal complex is prepared separately, a known method disclosed in J. Am. Chem. Soc., 1995, 117, p7562 can be applied as a catalyst synthesis method. For example, by heating an optically active nitrogen-containing compound and a Group VIII metal in the periodic table in a solvent such as 2-propanol in the presence of a base such as triethylamine, the optically active nitrogen-containing compound is coordinated to the Group VIII metal. A homogeneous metal complex is obtained. This may be used as it is, and may be isolated as crystals by a known method disclosed in Angew. Chem. Int. Ed. Engl. 1997, 36, p285. In addition, when preparing a chloride complex in this asymmetric metal complex, bases, such as the said triethylamine, are used, However, When preparing an amide complex and a hydride complex, a base is unnecessary.

Examples of the asymmetric metal complex prepared in advance in this way include chloride complexes, amide complexes, hydride complexes, and the like, and specifically include the following compounds.
Specific examples of ruthenium chloride complexes having optically active 1,2-diphenylethylenediamine as a ligand include chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine]. Benzene ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] benzene ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2 -Diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(S, S) -N- (P-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chromium B [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) Ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(R, R) -N- (p-toluene) Sulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) 1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene ) Ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [(R, R) -N- ( p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [ (S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5 -Triethylbenzene) ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(S, S)- N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [( , R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) ) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1 , 2,3,4-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) Ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene Ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl)- 1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Chloro [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, chloro [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, chloro [(S , S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [ (S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1 , 2-Dimethylbenzene) ruthenium, chloro [(S, S) -N-methanesulfonate -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [ (S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1 , 4-Dimethylbenzene) ruthenium, chloro [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(R, R) -N-methanesulfonyl-1, 2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(S, S) -N-methanesulfonyl-1, -Diphenylethylenediamine] (mesitylene) ruthenium, chloro [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N-methanesulfonyl-1,2 -Diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [ (S, S) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(R, R) -N- (methanesulfonyl) -1,2 -Diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(S, S ) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,3 , 5-triethylbenzene) ruthenium, chloro [(S, S) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (Methanesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (methanesulfonyl) -1,2 -Diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (methanesulfonyl) 1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (1,2,3 , 4-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, chloro [(S , S) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(R, R) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (pentamethyl Benzene) ruthenium, chloro [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (hexa Methylbenzene) ruthenium, chloro [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Chloro [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, chloro [ (S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) Ruthenium, chloro [(S, S) -N-trifluoromethanesulfonate] -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1 , 2-diphenylethylenediamine] (1, -Dimethylbenzene) ruthenium, chloro [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine ] (P-cymene) ruthenium, chloro [(R, R) N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(R , R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3- Trimethylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [(S, S) -N-trifluoromethane Sulfonyl-1,2-diphenylethyl Diamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [( S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine ] (1,3,5-triethylbenzene) ruthenium, chloro [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphe Ruethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3,5-tetramethyl Benzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- Trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1, 2,3,4-tetramethylbenzene) ruthenium, chloro [(S, S) -N-trifluoro Tansulfonyl-1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, chloro [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium ,

Chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl)- 1,2-diphenylethylenediamine] benzeneruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2- Diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenes) (Lufonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1, 3-dimethylbenzene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(S, S ) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-tert-butylbenzene) Zensulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) Ruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(R, R) -N- (4-tert-butyl Benzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3- Trimethylbenzene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenyl Ethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene ) Ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(S, S)- N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(S, S) -N- (4-tert Butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2 -Diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2 , 3,5-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene ) Ruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2, 3,4-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) Ruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(R, R) -N- (4-tert -Butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethyl Benzene) ruthenium, chloro [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenyl Ethylenediamine] (hexamethylbenzene) ruthenium,

Chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, chloro [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine ] Benzene ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [ (R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethyl) Benzene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(R, R) -N- (1 -Naphtylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4 -Dimethylbenzene) ruthenium, chloro [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(S, S) -N- (1-Naphtylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(R, R) -N- (1-naphthyl) (Rufonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(R , R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] ( 1,2,3-trimethylbenzene) ruthenium, chloro [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [( S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trime Rubenzene) ruthenium, chloro [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium , Chloro [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-teto Methylbenzene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(R, R ) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl)- 1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2 , 3,4-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] Pentamethylbenzene) ruthenium, chloro [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(S, S) -N- (1- Naphthylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, chloro [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Chloro [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, chloro [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine ] Benzene ruthenium, chloro [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [ (R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethyl) Benzene) ruthenium, chloro [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(R, R) -N- (2 -Naphtylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4 -Dimethylbenzene) ruthenium, chloro [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(S, S) -N- (2-Naphtylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(R, R) -N- (2-naphthyl) Lufonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(R , R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] ( 1,2,3-trimethylbenzene) ruthenium, chloro [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [( S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trime Rubenzene) ruthenium, chloro [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(S, S) -N- (2-Naphtylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium , Chloro [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-teto Methylbenzene) ruthenium, chloro [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(R, R ) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (2-naphthylsulfonyl)- 1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2 , 3,4-Tetramethylbenzene) ruthenium, chloro [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] Pentamethylbenzene) ruthenium, chloro [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(S, S) -N- (2- Naphthylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, chloro [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2- Diphenylethylenediamine] benzeneruthenium, chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(R, R) -N- (4- Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene ) Ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenyl Ruethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [ (R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene ) Ruthenium, Chloro [(S, S) -N- (4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine ] (P-cymene) ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, Chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [(R, R) -N- (4- Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [( , S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3 5-triethylbenzene) ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(S, S ) -N- (4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylben N) ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(S, S ) -N- (4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) ) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] ( 1,2,3,4-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenyl Ethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(S, S) -N- (4-amylbenzenesulfonyl) -1 , 2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, chloro [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine ] Benzene ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [ (R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1 2-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(R, R) -N -(4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] ( 1,4-dimethylbenzene) ruthenium, chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(R, R)- -(4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium , Chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2 -Diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) Ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylene Diamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, Chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(R, R) -N- (4-biphenyl) Sulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2 , 4,5-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenyl Ethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5- Tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-biphenyl) Sulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [ (S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, chloro [(R, R) -N- (4-biphenylsulfonyl) -1,2- Diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, chloro [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2- Diphenylethylenediamine] benzeneruthenium, chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(R, R) -N- (4- Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene ) Ruthenium, Chloro [(R, R) -N- (4-Isopropylbenzene) Nzensulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3 -Dimethylbenzene) ruthenium, chloro [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(S, S) -N -(4-Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine ] (1,4-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-iso Propylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium , Chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(R, R) -N- (4-isopropylbenzenesulfonyl) -1 , 2-Diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [ (R, R) -N- (4-Isopropylbenzenesulfonyl) 1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4 -Trimethylbenzene) ruthenium, chloro [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(R, R) -N- (4-isopropylbenzenesulfonyl) -1, 2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [( , S) -N- (4-Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-isopropyl Benzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine ] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5- Tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphe Ruethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3, 4-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(R, R) -N- (4-Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethyl Benzene) ruthenium, chloro [(R, R) -N- (4-isopropylbenzene) Zensuruhoniru) -1,2-diphenyl ethylenediamine] (hexamethylbenzene) ruthenium,

Chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine ] Benzene ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [ (R, R) -N- (4-Ethylbenzenesulfonyl) -1,2-diphenyl Ruethylenediamine] (1,2-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [( R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1, 2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] p-cymene) ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(S, S) -N- (4- Ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1, 2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, chloro [(S, ) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2 -Diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) Ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(S, S) -N- (4 -Ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene ) Ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(S, S)- N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1, 2-Diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3 4-tetramethylbenzene) ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenyl ester Rangeamine] (1,2,3,4-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2 -Diphenylethylenediamine] (hexamethylbenzene) ruthenium, chloro [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium.
In addition to chloride complexes, bromide complexes and iodide complexes can be used as catalysts as well.

  Specific examples of ruthenium amide complexes having optically active 1,2-diphenylethylenediamine as a ligand include [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium. [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (Methylbenzene) ruthenium, [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(R, R) -N- (p-toluene) [Rufonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene ) Ruthenium, [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(S, S) -N- (p-toluenesulfonyl) ) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) Ruthenium, [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, [( R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine ] (Mesitylene) ruthenium, [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(S, S) -N- (p-toluenesulfonyl)- 1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethyl Benzene) ruthenium, [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-tri Tylbenzene) ruthenium, [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(S, S) -N- (p -Toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1, 3,5-triethylbenzene) ruthenium, [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [(R , R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) rutenium , [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(R, R) -N- (p -Toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene ) Ruthenium, [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [(R, R) -N- ( -Toluenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, (R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

[(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2-dimethylbenzene) Ruthenium, [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] ( , 3-Dimethylbenzene) ruthenium, [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(S, S) -N-methanesulfonyl-1 , 2-Diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(S, S ) -N-methanesulfonyl-1,2-diphenylethylenediamine] (p-cymene) ruthenium, [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (p-cymene) ruthenium, [(S , S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(R, R) -N- Tansulfonyl-1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(S, S) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (1 , 2,4-trimethylbenzene) ruthenium, [(R, R) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(S, S)- N-methanesulfonyl-1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(S, S) -N- (methanesulfonyl) -1,2-diphenyl Ethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [(R, R) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene ) Ruthenium, [(S, S) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(R, R) -N- (methane Sulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(S, S) -N- (methanesulfonyl) -1,2 Diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(R, R) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethyl Benzene) ruthenium, [(S, S) -N- (methanesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [(R, R) -N- (methanesulfonyl) -1,2- Diphenylethylenediamine] (pentamethylbenzene) ruthenium, [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, [(R, R) -N-methanesulfonyl-1, 2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

 [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [( S, S) -N-trifluoromethanesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2-Dimethylbenzene) ruthenium [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(R, R) -N-trifluoro Lomethanesulfonyl-1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (p-cymene) ruthenium, [(R , R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenedia (P-cymene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(R, R) -N-trifluoromethanesulfonyl-1,2 -Diphenylethylenediamine] (mesitylene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(R, R) -N- Trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,4- Trimethylbenzene) ruthenium, [(R, R) -N-trifluoromethane Ruphonyl-1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,3,5-triethylbenzene ) Ruthenium, [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1, 2-Diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,4,5-tetra Methylbenzene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1 2-Diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3,5-tetra Methylbenzene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(R, R) -N-trifluoro Lomethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (pentamethylbenzene) Ruthenium, [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenyl Ruethylenediamine] (pentamethylbenzene) ruthenium, [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, [(R, R) -N-trifluoromethanesulfonyl- 1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

[(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1, 2-diphenylethylenediamine] benzeneruthenium, [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(R, R) -N- ( 4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1 , 2-Dimethylbenzene) ruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenyl ester Rangeamine] (1,2-dimethylbenzene) ruthenium, [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [ (R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(S, S) -N- (4-tert-butyl Benzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1, 4-dimethylbenzene) ruthenium, [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-Si Men) ruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, [(S, S) -N- (4-tert -Butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [ (S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(R, R) -N- (4-tert -Butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(S, S) -N- (4-te rt-Butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenyl Ethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) Ruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(S, S) -N- ( 4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [ R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [(S, S) -N- (4 -Tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1 , 2-Diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1, 2,3,4-tetramethylbenzene) ruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1, , 3,4-tetramethylbenzene) ruthenium, [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2- Diphenylethylenediamine] (hexamethylbenzene) ruthenium, [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

[(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] benzene Ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(R, R) -N- (1-naphthylsulfonyl) -1,2 -Diphenylethylenediamine] (methylbenzene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(R, R)- N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(R, R)- N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] ( p-cymene) ruthenium, [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) rute [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(R, R) -N- (1-naphthylsulfonyl) -1,2- Diphenylethylenediamine] (mesitylene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(R, R)- N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine ] (1,2,4-trimethylbenzene) ruthenium, [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylene Diamine] (1,2,4-trimethylbenzene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [ (R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl)- 1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2, 4,5-tetramethylbenzene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3 5-tetramethylbenzene) ruthenium, [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(R, R) -N- (1-naphthylsulfonyl)- 1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) Ruthenium, [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, [(R, R) -N- (1-naphthylsulfonyl) -1,2- Diphenylethylenediamine] (hexamethylbenzene) ruthenium,

[(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] benzene Ruthenium, [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(R, R) -N- (2-naphthylsulfonyl) -1,2 -Diphenylethylenediamine] (methylbenzene) ruthenium, [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(R, R)- N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(R, R)- N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] ( p-cymene) ruthenium, [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) rutheni [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(R, R) -N- (2-naphthylsulfonyl) -1,2- Diphenylethylenediamine] (mesitylene) ruthenium, [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(R, R)- N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine ] (1,2,4-trimethylbenzene) ruthenium, [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylene Diamine] (1,2,4-trimethylbenzene) ruthenium, [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [ (R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(S, S) -N- (2-naphthylsulfonyl)- 1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2, 4,5-tetramethylbenzene) ruthenium, [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3, -Tetramethylbenzene) ruthenium, [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(S, S ) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(R, R) -N- (2-naphthylsulfonyl) -1 , 2-Diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [ S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine ] (Hexamethylbenzene) Ruthenium,

[(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine ] Benzene ruthenium, [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [( R, R) -N- (4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethyl) Rubenzene) ruthenium, [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(R, R) -N- (4- Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4 -Dimethylbenzene) ruthenium, [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(S, S) -N- ( 4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, [(R, R) -N- (4-amylben Sulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(R , R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [( S, S) -N- (4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4- Trimethylbenzene) ruthenium, [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(S, S) -N- (4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(R, R) -N- (4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine ] (1,3,5-triethylbenzene) ruthenium, [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) Ruthenium, [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4 5-tetramethylbenzene) ruthenium, [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(R , R) -N- (4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(S, S) -N- (4-amylbenzene) (Sulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] ( 1,2,3,4-tetramethylbenzene) ruthenium, [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylene Diamine] (pentamethylbenzene) ruthenium, [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [(S, S) -N- ( 4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

 [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] benzene Ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(R, R) -N- (4-biphenylsulfonyl) -1,2 -Diphenylethylenediamine] (methylbenzene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(R, R)- N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium , [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(R, R) -N- (4-biphenylsulfonyl)- 1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1 , 2-Diphenylethylenediamine] (p-cymene) ruthenium, [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenedia (P-cymene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(R, R) -N- (4-biphenyl) (Sulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(R, R) -N- (4-biphenyls Phonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,3, 5-triethylbenzene) ruthenium, [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(S, S) -N -(4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [(R, R) -N- (4-biphenylsulfonyl) -1,2- Diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1 2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3, 5-tetramethylbenzene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl)- 1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphe Ruethylenediamine] (pentamethylbenzene) ruthenium, [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, [(R, R) -N- ( 4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

 [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine ] Benzene ruthenium, [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [( R, R) -N- (4-Isopropylbenzenesulfonyl) -1,2-diph Nylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(R R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(S, S) -N- (4-isopropylbenzenesulfonyl) -1, 2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [ (S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenedi Min] (p-cymene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, [(S, S) -N- ( 4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [( S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [( S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5 -Triethylbenzene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(S, S) -N -(4-Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetra Tylbenzene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [(S, S)- N- (4-Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1 , 2-Diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2, 3,4-tetramethylbenzene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2- Diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [ (R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2, -Diphenylethylenediamine] (hexamethylbenzene) ruthenium, [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

 [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzene Ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, [(R, R) -N- (4-ethylbenzenesulfonyl) -1, 2-diphenylethylenediamine] (methylbenzene) ruthenium, [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, [(R, R) -N- (4-Ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2 Dimethylbenzene) ruthenium, [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(R, R) -N- (4- Ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethyl Benzene) ruthenium, [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, [(S, S) -N- (4-ethylbenzene Sulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, [(R, R) -N- (4-ethyl) Nsenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1, 2,3-trimethylbenzene) ruthenium, [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2 4-trimethylbenzene) ruthenium, [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, [(S, S) -N -(4-Ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2 , 4,5-tetramethylbenzene) ruthenium, [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [ (R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, [(S, S) -N- (4-ethylbenzene Sulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1 , 2,3,4-tetramethylbenzene) ruthenium, [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenyl Ethylenediamine] (pentamethylbenzene) ruthenium, [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, [(S, S) -N- (4 -Ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium It is done.

  Examples of ruthenium hydride complexes having optically active 1,2-diphenylethylenediamine as a ligand include hydrido [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] benzene ruthenium, hydride [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, hydride [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (Methylbenzene) ruthenium, hydride [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(S, S) -N- (p-toluene) Sulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium Hydride [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydride [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) Ruthenium, hydride [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(R, R) -N- (p-toluene) Sulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(S, S) -N- (p-tolue) Sulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydride [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydride [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenyl Ethylenediamine] (mesitylene) ruthenium, hydride [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydride [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethyl Nzen) ruthenium, hydrido [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydrido [(R, R) -N- (P-Toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydride [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [ (S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-teto Methylbenzene) ruthenium, hydrido [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, hydride [(S, S ) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(R, R) -N- (p-toluenesulfonyl)- 1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2, , 3,4-tetramethylbenzene) ruthenium, hydrido [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethyl Diamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [ (R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [(S, S) -N- (p-toluenesulfonyl) -1,2- Diphenylethylenediamine] (hexamethylbenzene) ruthenium, hydrido [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Hydride [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, hydrido [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, hydride [(S , S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [ (S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydride [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1 , 2-Dimethylbenzene) ruthenium, hydride [(S, S) -N Methanesulfonyl-1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, Hydride [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, Hydride [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,4-Dimethylbenzene) ruthenium, hydrido [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydrido [(R, R) -N-methanesulfonyl- 1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydride [(S, S) N-methanesulfonyl-1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(S, S)- N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydride [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2,3 -Trimethylbenzene) ruthenium, hydrido [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydrido [(R, R) -N-methanesulfonyl -1,2-diphenylethylenediamine] (1,2,4-trimethylbenze N) ruthenium, hydrido [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(R, R) -N-methanesulfonyl-1 , 2-Diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2,4,5-tetramethyl) Ruthenium, hydride [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2,4,5-tetramethyl) ruthenium, hydride [(S, S) -N-methanesulfonyl-1 , 2-Diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(R, R) -N-meta Sulfonyl-1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2, 3,4-tetramethyl) ruthenium, hydride [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (1,2,3,4-tetramethyl) ruthenium, hydride [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [(R, R) -N-methanesulfonyl-1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [( S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (hexamethylbenzene) Zen) ruthenium, hydrido [(R, R)-N-methanesulfonyl-1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Hydride [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, hydrido [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] benzeneruthenium, hydride [ (S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (methylbenzene) Ruthenium, hydride [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydride [(R, R) -N-trifluoromethanesulfonyl-1,2, -Diphenylethylene Diamine] (1,2-dimethylbenzene) ruthenium, hydride [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,4- Dimethylbenzene) ruthenium, hydrido [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydrido [(S, S) -N-trifluoromethanesulfonyl- 1,2-diphenylethylenediamine] (p-cymene) rute Nitrogen, hydrido [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydrido [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine ] (Mesitylene) ruthenium, hydride [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(S, S) -N-trifluoromethanesulfonyl-1,2- Diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydride [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydride [ (S, S) -N-trifluorome Sulfonyl-1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydride [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,4- Trimethylbenzene) ruthenium, hydrido [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydrido [(R, R) -N-trifluoromethane Sulfonyl-1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,4,5 -Tetramethyl) ruthenium, hydrido [(R, R) -N-tri Fluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,4,5-tetramethyl) ruthenium, hydride [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2 , 3,5-tetramethylbenzene) ruthenium, hydride [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [( S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (1,2,3,4-tetramethyl) ruthenium, hydride [(R, R) -N-trifluoromethanesulfonyl-1,2- Diphenylethylenediamine] (1,2,3,4-tetramethyl) ruthenium, hydride [ S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydrido [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (pentamethylbenzene ) Ruthenium, hydride [(S, S) -N-trifluoromethanesulfonyl-1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, [(R, R) -N-trifluoromethanesulfonyl-1,2-diphenyl Ethylenediamine] (hexamethylbenzene) ruthenium,

Hydride [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, hydride [(R, R) -N- (4-tert-butylbenzenesulfonyl)- 1,2-diphenylethylenediamine] benzeneruthenium, hydride [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydrido [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2- Diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydride [(R, R) -N- (4-tert- Tylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydrido [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] ( 1,3-dimethylbenzene) ruthenium, hydride [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(S , S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(R, R) -N- (4-tert-butylbenzene) Sulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydride [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2 -Diphenylethylenediamine] (p-cymene) ruthenium, hydride [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydrido [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenyl Ethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydride [(R, R) -N- (4-tert-butyl) Nsenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydride [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydrido [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium Hydride [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(R, R) -N- (4-tert-Butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ) Ruthenium, hydrido [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, hydride [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4- tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydrido [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1 , 2-Diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4-tert-butylbenzene Sulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydrido [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenyl Ethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium Hydride [(R, R) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [(S, S) -N- (4-tert- Butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, hydride [( , R) -N- (4-tert- butyl-benzenesulfonyl) -1,2-diphenyl ethylenediamine] (hexamethylbenzene) ruthenium,

Hydride [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, hydride [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine ] Benzene ruthenium, hydride [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydride [ (R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] ( , 2-Dimethylbenzene) ruthenium, hydrido [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydrido [(R, R)- N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(S, S ) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydride [( R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydrido [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenyl Ethylenediamine] (mesitylene) ruthenium, hydrido [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydrido [(S, S) -N- (1-naphthyl) Sulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydrido [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2 , 3-Trimethylbenzene) ruthenium, hydrido [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphe Nylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydrido [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium Hydride [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(R, R) -N- (1- Naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1, 2,4,5-tetramethylbenzene) ruthenium, hydrido [(R, R) -N- (1-naphthylsulfonyl) -1, -Diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3, 5-tetramethylbenzene) ruthenium, hydride [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [( S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(R, R) -N- (1-naphthyl) Sulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(S, S) -N (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [(R, R) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) Ruthenium, hydride [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, hydride [(R, R) -N- (1-naphthylsulfonyl)- 1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Hydride [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, hydrido [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine ] Benzene ruthenium, hydride [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydride [ (R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] ( , 2-Dimethylbenzene) ruthenium, hydride [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(R, R)- N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(S, S ) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydride [(R , R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydrido [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine ] (Mesitylene) ruthenium, hydride [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(S, S) -N- (2-naphthylsulfonyl) ) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydride [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2, 3-trimethylbenzene) ruthenium, hydrido [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenyl Ethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydride [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, Hydrido [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydrido [(R, R) -N- (2-naphthyl) Sulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2 , 4,5-tetramethylbenzene) ruthenium, hydrido [(R, R) -N- (2-naphthylsulfonyl) -1,2- Phenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5 -Tetramethylbenzene) ruthenium, hydride [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(S , S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(R, R) -N- (2-naphthylsulfonyl) ) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(S, S) -N- ( -Naphthylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydrido [(R, R) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, Hydride [(S, S) -N- (2-naphthylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, hydride [(R, R) -N- (2-naphthylsulfonyl) -1, 2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Hydride [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, hydride [(R, R) -N- (4-amylbenzenesulfonyl) -1,2- Diphenylethylenediamine] benzeneruthenium, hydrido [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(R, R) -N- (4- Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydrido [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene ) Ruthenium, hydride [(R, R) -N- (4-amylbenzenesulfonyl) -1 2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydride [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, Hydride [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(S, S) -N- (4-amylbenzene Sulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4- Dimethylbenzene) ruthenium, hydride [(S, S) -N- (4-amylbenzenesulfonyl) -1,2- Diphenylethylenediamine] (p-cymene) ruthenium, hydride [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydride [(S, S)- N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydrido [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) Ruthenium, hydrido [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydrido [(R, R) -N- ( 4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-tri Methylbenzene) ruthenium, hydrido [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydrido [(R, R)- N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydride [(S, S) -N- (4-amylbenzenesulfonyl) -1,2 -Diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene ) Ruthenium, hydrido [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenyl Tylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, hydride [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4, 5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [ (R, R) -N- (4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4 -Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(R R) -N- (4-Amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4-amylbenzene) Sulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [(R, R) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [(S, S) -N- (4-amylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, hydride [(R, R) -N- (4-amylbenzenesulfonyl) -1 , 2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Hydrido [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, hydride [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine ] Benzene ruthenium, hydride [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydride [ (R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylene Diamine] (1,2-dimethylbenzene) ruthenium, hydride [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(R , R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(S, S) -N- (4-biphenylsulfonyl) -1,2 -Diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [ (S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) l Tenium, hydride [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydride [(S, S) -N- (4-biphenylsulfonyl)- 1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(S, S) -N -(4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydrido [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine ] (1,2,3-trimethylbenzene) ruthenium, hydride [(S, S) -N- (4-Bif Sulfonylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydride [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1, 2,4-trimethylbenzene) ruthenium, hydride [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(S, S) -N- (4-biphenylsulfonyl) -1, 2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, hydride [(R, ) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4-biphenylsulfonyl)- 1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2 , 3,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, Hydride [(R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-teto Methylbenzene) ruthenium, hydrido [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydrido [(R, R) -N- (4-biphenyl) Sulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, hydride [ (R, R) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

 Hydrido [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, hydrido [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2- Diphenylethylenediamine] benzeneruthenium, hydrido [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydrido [(R, R) -N- (4- Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene ) Ruthenium, hydride [(R, R) -N- (4 Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydrido [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1, 3-dimethylbenzene) ruthenium, hydride [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(S, S)- N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydrido [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenyl Ethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydride [(R, R) -N- (4-isopropylbenzenesulfonyl) -1 , 2-Diphenylethylenediamine] (p-cymene) ruthenium, hydride [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1 , 2,3-Trimethylbenzene) ruthenium, hydride [(R, R)- N- (4-Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydride [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2 -Diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydride [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene ) Ruthenium, hydrido [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydrido [(R, R) -N- (4-Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] ( , 3,5-triethylbenzene) ruthenium, hydride [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, Hydride [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4-Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(R, R) -N- (4-isopropylbenzenesulfonyl) -1, 2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(S, S ) -N- (4-Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydrido [(R, R) -N- (4-isopropylbenzenesulfonyl) ) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] ( Pentamethylbenzene) ruthenium, hydride [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [(S, S) -N- (4 -Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexa Methylbenzene) ruthenium, hydride [(R, R) -N- (4-isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium,

Hydrido [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] benzeneruthenium, hydride [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine ] Benzene ruthenium, hydride [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (methylbenzene) ruthenium, hydride [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydride [ (R, R) -N- (4-ethylbenzenesulfonyl)- , 2-diphenylethylenediamine] (1,2-dimethylbenzene) ruthenium, hydride [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, Hydride [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3-dimethylbenzene) ruthenium, hydride [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium, hydride [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) Ruthenium, hydride [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2- Diphenylethylenediamine] (p-cymene) ruthenium, hydrido [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (p-cymene) ruthenium, hydride [(S, S) -N -(4-Ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, hydride [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3-trimethylbenzene) ruthenium, hydride [(R, R) -N- (4-ethylbenzenesulfonyl) ) -1,2-diphenylethylenediamine] (1,2,3-tri Methylbenzene) ruthenium, hydrido [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydride [(R, R) -N -(4-Ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4-trimethylbenzene) ruthenium, hydride [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine ] (1,3,5-triethylbenzene) ruthenium, hydride [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, hydride [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenyl Tylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, hydride [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5 -Tetramethylbenzene) ruthenium, hydrido [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(R , R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,5-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4-ethylbenzenesulfonyl) ) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(R , R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (1,2,3,4-tetramethylbenzene) ruthenium, hydride [(S, S) -N- (4-ethylbenzenesulfonyl) ) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (pentamethylbenzene) ruthenium, hydride [( S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] (hexamethylbenzene) ruthenium, hydride [(R, R) -N- (4-ethylbenzenesulfonyl) -1,2-diphenyl Ethylenediamine] (hexamethylbenzene) ruthenium. Among them, preferred asymmetric metal complexes include chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(R, R) -N- (p -Toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,4-dimethylbenzene) ruthenium , Chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (1,2,4,5-tetramethylbenzene) ruthenium, chloro [(S, S) -N- (P-Toluenesulfonyl) -1,2-diphenylethylenediamine] (1,3,5-triethylbenzene) ruthenium, chloro [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (p-cymene) ruthenium, chloro [(S, S) -N-methanesulfonyl-1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-cyclohexanediamine] (p-cymene) ruthenium, chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2- Diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (1-naphthylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (2- Naphthylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (4-amylbe Nzensulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (4-biphenylsulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (4-Isopropylbenzenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium, chloro [(S, S) -N- (4-ethylbenzenesulfonyl) -1,2-diphenylethylenediamine] ( Mesitylene) ruthenium.

In addition, ruthenium chloride complexes, amide complexes, and hydride complexes having optically active 1,2-cyclohexanediamine as a ligand may include complexes similar to the above specific examples having 1,2-diphenylethylenediamine as a ligand. it can. Among them, chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-cyclohexanediamine] (p-cymene) ruthenium is preferable.
In addition to chloride complexes, bromide complexes and iodide complexes can be used as catalysts as well.

  The amount of the asymmetric metal complex used is usually 10 to 100,000, preferably 100 to 2,000 in terms of the molar ratio (S / C) of the asymmetric metal complex to the raw material (general formula (A)). Most preferably, it is 100-500.

  The hydrogen donor in the present invention donates hydrogen to a carbonyl group and a heteroaromatic ring, and preferable examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, sec-butyl. Examples thereof include alcohol compounds having a hydrogen atom at the α-position such as alcohol and benzyl alcohol, formic acid, and formate salts such as sodium and potassium, preferably 2-propanol and formic acid.

  The amount of hydrogen donor relative to the substrate is usually in the range of 1 mol to a large excess (usually 1000 mol), and generally when alcohol is used as the hydrogen donor, it is also used as a solvent in a large excess (usually 1000 mol). When formic acid is used as a hydrogen donor, it is used in a range of 1 to 20 moles, particularly preferably 8 to 20 moles.

Examples of the base used in the production method of the present invention include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkalis such as lithium methoxide, sodium methoxide, sodium ethoxide and potassium isopropoxide. Illustrative are organic amines such as metal alkoxides, trimethylamine, triethylamine, triisopropylamine. Those preferably used are sodium hydroxide, potassium hydroxide and triethylamine which is a tertiary amine.

The base is preferably used in an excess amount, for example, a molar ratio of 1 to 1000 moles, more preferably 1 to 100 moles, relative to the asymmetric metal complex. In general, when alcohol is used as a hydrogen donor, potassium hydroxide is used in an amount of 1 to 10 moles, and when formic acid is used as a hydrogen donor, triethylamine is used in an amount of 1 to 1000 moles.
In addition, the manufacturing method of this invention can be implemented in absence of a base, when a metal amide complex and a hydride complex are used.

  When a chloride complex or the like is used in the asymmetric metal complex of the present invention, an optically active alcohol having a nitrogen-containing heterocycle is produced in the presence of a base in order to express the function of a hydrogen donor. Suitable combinations of the base and hydrogen donor used in this case include a combination of 2-propanol and potassium hydroxide or sodium hydroxide, and a combination of formic acid and triethylamine. A combination of formic acid and triethylamine is most preferred because the reduction reaction proceeds efficiently.

  When formic acid and an organic amine are used in combination, a mixture of formic acid and an organic amine may be prepared and used in advance, or may be prepared and used in a reaction vessel. For example, when formic acid and triethylamine are used, the amount used is determined by considering the stability of the raw material compound with respect to acid and base, and considering the reactivity, by changing the formic acid and triethylamine addition amount, It is necessary to make the amount of triethylamine. In the present invention, in addition to the carbonyl group, the nitrogen-containing heteroaromatic ring is also reduced. Therefore, it is preferable to use the formic acid in a range of 4.4 to 44 mole ratio and triethylamine in the range of 2.6 to 26 mole ratio relative to the substrate. . In order to obtain a target product with high yield and high optical purity, formic acid is more preferably in a 6.6-22 molar ratio and triethylamine is in a 5.2-13 molar ratio.

In the present invention, the hydrogen donor itself is usually used as a reaction solvent, but in order to improve the solubility of the raw materials, aromatic compounds such as toluene and xylene, halogen compounds such as dichloromethane, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, Organic compounds such as acetonitrile can be used alone or in combination. In particular, it is preferable to add dimethylformamide, acetonitrile or the like as a reaction solvent because it contributes to an improvement in the reaction yield.
The reaction temperature in the present invention can be about −20 ° C. to 100 ° C. in consideration of economy. More practically, the reaction can be carried out at a room temperature of 20 ° C. to 60 ° C.

Further, the reaction pressure is not particularly limited, and it is usually performed under 0.5 atm to 2 atm, preferably 1 atm.
The reaction time varies depending on the reaction conditions such as reaction substrate concentration, temperature, pressure, etc., but the reaction is completed in several minutes to 100 hours.
The product can be purified by a known method such as column chromatography, distillation or recrystallization.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, it is not restrict | limited to a following example. In the examples, ee% represents the enantiomeric excess, and S / C represents the molar ratio of the substrate to the catalyst (molar ratio of the substrate to ruthenium).

[Example 1]
(R) -6- [1- [2- (4-Cyanophenyl) -2-hydroxyethyl] -1,2,5,6-tetrahydropyrid-4-yl] -4,5-dihydropyridazine-3 (2H) -ON manufacturing
1- (4-Cyanophenylcarbonylmethyl) -4- (4,5-dihydropyridazine-3 (2H) -one-6-yl) pyridinium bromide 3.50 g (8.77 mmol), triethylamine 9.6 ml (69 mmol), formic acid 4.4 ml (117 mmol) (formic acid / triethylamine = 13.2 / 7.8 to substrate molar ratio), asymmetric metal complex chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium 27.6 mg (4.43 × 10 ⁻² mmol, S / C = 200) was placed in a 50 ml Schlenk under an argon atmosphere and stirred at 40 ° C. for 24 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution to make it basic, and the precipitated powder was collected by filtration to obtain the desired product in an isolated yield of 94%. As a result of measuring optical purity with a CHIRALCEL OD column (manufactured by Daicel, eluent; n-hexane: ethanol = 65: 35), it was 91% ee.

[Example 2]
1- (4-Cyanophenylcarbonylmethyl) -4- (4,5-dihydropyridazine-3 (2H) -one-6-yl) pyridinium bromide 200 mg (0.5 mmol) The reaction was carried out under the same conditions as in Example 1 except that the homogeneous metal complex was changed as follows. The results are shown in Table-1.

Example 3
1- (4-Cyanophenylcarbonylmethyl) -4- (4,5-dihydropyridazin-3 (2H) -on-6-yl) pyridinium bromide 200 mg (0.5 mmol) The reaction was performed under the same conditions as in Example 1 except that the above was changed. The results are shown in Table-2.

Example 4
1- (4-Cyanophenylcarbonylmethyl) -4- (4,5-dihydropyridazine-3 (2H) -one-6-yl) pyridinium bromide 400 mg (1 mmol) was changed to the reaction temperature as follows: The reaction was performed under the same conditions as in Example 1 except for the above. The results are shown in Table-3.

Example 5
(R) -6- [1- [2- (4-Cyanophenyl) -2-hydroxyethyl] -1,2,5,6-tetrahydropyrid-4-yl] -4,5-dihydropyridazine-3 (2H) -ON manufacturing
1- (4-Cyanophenylcarbonylmethyl) -4- (4,5-dihydropyridazin-3 (2H) -one-6-yl) pyridinium bromide 400 mg (1.00 mmol), triethylamine 1.1 ml (7.9 mmol), formic acid 0.5 ml (13.2 mmol) (formic acid / triethylamine = 13.2 / 7.8 to substrate molar ratio), asymmetric metal complex chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) Ruthenium 3.2 mg (5.14 × 10 ⁻³ mmol, S / C = 200) and acetonitrile 1.5 ml as a solvent were placed in a 20 ml Schlenk under an argon atmosphere and stirred at 40 ° C. for 24 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution to make it basic, and then the precipitated powder was collected by filtration to obtain the desired product in an isolated yield of 93.0%. As a result of measuring the optical purity with a CHIRALCEL OD column (manufactured by Daicel, eluent; n-hexane: ethanol = 65: 35), it was 90.9% ee.

Example 6
The reaction was carried out under the same conditions as in Example 5 except that the solvent acetonitrile was changed to dimethylformamide. As a result, the isolated yield was 93.6% and the optical purity was 90% ee.

Example 7
1- (4-Cyanophenylcarbonylmethyl) -4- (4,5-dihydropyridazine-3 (2H) -one-6-yl) pyridinium bromide 1.0 g (2.5 mmol) vs. triethylamine 2.7 ml (19.4 mmol) , 1.3 ml (34.4 mmol) of formic acid (formic acid / triethylamine = 13.2 / 7.8 to substrate molar ratio) and 3.0 ml of acetonitrile, except that S / C and reaction temperature were changed as follows under the conditions of Example 5. Reaction was performed. The results are shown in Table-4.

Example 8
(R) -6- [1- [2- (4-Cyanophenyl) -2-hydroxyethyl] -1,2,5,6-tetrahydropyrid-4-yl] -4,5-dihydropyridazine-3 (2H) -ON manufacturing
1- (4-Cyanophenylcarbonylmethyl) -4- (4,5-dihydropyridazin-3 (2H) -one-6-yl) pyridinium bromide 270 mg (0.67 mmol), triethylamine 0.74 ml (5.3 mmol), formic acid 0.34 ml (9.0 mmol) (formic acid / triethylamine = 13.2 / 7.8 to substrate molar ratio), asymmetric metal complex chloro [(S, S) -N- (4-tert-butylbenzenesulfonyl) -1,2-diphenylethylenediamine] (Mesitylene) ruthenium 2.2 mg (3.31 × 10 ⁻³ mmol, S / C = 200) and 0.8 ml of acetonitrile as a solvent were placed in a 20 ml Schlenk under an argon atmosphere and stirred at 40 ° C. for 24 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution to make it basic, and then the precipitated powder was collected by filtration to obtain the desired product in an isolated yield of 96.5%. As a result of measuring the optical purity with a CHIRALCEL OD column (manufactured by Daicel, eluent; n-hexane: ethanol = 65: 35), it was 92.7% ee.

Example 9
1- (4-Cyanophenylcarbonylmethyl) -4- (4,5-dihydropyridazin-3 (2H) -one-6-yl) pyridinium bromide 270 mg (0.67 mmol), S / C = 200 The reaction was carried out under the same conditions as in Example 8 except that the homogeneous metal complex was changed as follows. The results are shown in Table-5.

Example 10
The reaction was performed under the conditions of Example 8 except that the S / C and reaction temperature were changed as follows. The results are shown in Table-6.

Example 11
(S) -6- [1- [2- (4-Cyanophenyl) -2-hydroxyethyl] -1,2,5,6-tetrahydropyrid-4-yl] -4,5-dihydropyridazine-3 (2H) -ON manufacturing
1- (4-Cyanophenylcarbonylmethyl) -4- (4,5-dihydropyridazine-3 (2H) -one-6-yl) pyridinium bromide 50.00 g (124.1 mmol), triethylamine 98.84 g (957 mmol), formic acid 76.09 g (1.620 mol) (formic acid / triethylamine = 13.1 / 7.7 to substrate molar ratio), asymmetric metal complex chloro [(R, R) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene ) 260.1 mg (4.18 × 10 ⁻¹ mmol, S / C = 300) of ruthenium and 158 ml of acetonitrile were placed in a 1 L four-necked flask under an argon atmosphere and stirred at 40 ° C. for 24 hours. After cooling to room temperature, the reaction solution was filtered, and the filtrate was washed with acetonitrile to obtain the desired product in an isolated yield of 85%. As a result of measuring the optical purity with a CHIRALCEL OD column (manufactured by Daicel, eluent; n-hexane: ethanol = 50: 50), it was 90.5% ee.

Example 12
Preparation of (R) -2- (4-methyl-1,2,5,6-tetrahydropyridin-1-yl) -1-phenylethanol Phenylcarbonylmethyl-4-methylpyridinium bromide 0.49 g (1.69 mmol), triethylamine 1.85 ml (13.3 mmol), 0.84 ml (22.3 mmol) formic acid (formic acid / triethylamine = 13.2 / 7.8 to substrate molar ratio), chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenyl Ethylenediamine] (mesitylene) ruthenium 5.43 mg (8.72 × 10 ⁻³ mmol, S / C = 200) and 2.0 ml of acetonitrile were placed in a 20 ml Schlenk under an argon atmosphere and stirred at 40 ° C. for 24 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution to make it basic, and then the precipitated powder was collected by filtration. The reaction yield was 60%, and the optical purity was measured with a CHIRALCEL OB-H column (manufactured by Daicel, eluent; n-hexane: 2-propanol: diethylamine = 99: 1: 0.1). Met.

Example 13
The reaction was conducted according to the conditions of Example 12 except that S / C was changed to 100. The reaction yield was 65% and the optical purity measured by HPLC was 98% ee.

Example 14
Preparation of 2- (2-methylpiperidin-1-yl) -1-phenylethanol Phenylcarbonylmethyl-2-methylpyridinium bromide 0.47 g (1.56 mmol), triethylamine 1.7 ml (12 mmol), formic acid 0.8 ml (21 mmol), chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium 4.96 mg (7.98 × 10 ⁻³ mmol, S / C = 200), acetonitrile 2.0 ml, argon Under an atmosphere, it was placed in a 20 ml Schlenk and stirred at 40 ° C. for 24 hours. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution to make it basic, and the reaction solution was extracted with chloroform. The chloroform solution was washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the desired product. The reaction yield was 50%.

Example 15
Preparation of 2- (3-methylpiperidin-1-yl) -1-phenylethanol Phenylcarbonylmethyl-3-methylpyridinium bromide 0.47 g (1.56 mmol), triethylamine 1.7 ml (12 mmol), formic acid 0.8 ml (21 mmol), chloro [(S, S) -N- (p-toluenesulfonyl) -1,2-diphenylethylenediamine] (mesitylene) ruthenium 4.94 mg (7.94 × 10 ⁻³ mmol, S / C = 200), acetonitrile 2.0 ml, argon Under an atmosphere, it was placed in a 20 ml Schlenk and stirred at 40 ° C. for 24 hours. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution to make it basic, and the reaction solution was extracted with chloroform. The chloroform solution was washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the desired product. The reaction yield was 60%.

  The optically active alcohol having a nitrogen-containing heterocycle obtained by the production method of the present invention is used to synthesize physiologically active substances, pharmaceuticals, particularly pharmaceutical intermediates of β-adrenergic effect blockers, agricultural chemicals, catalysts for asymmetric synthesis, etc. Useful for intermediates and the like. Therefore, the manufacturing method of the present invention greatly contributes to the development of such related industries.

Claims (9)

Formula (A)

(In the formula, R ¹ and R ² are an aromatic monocyclic or aromatic polycyclic hydrocarbon group which may have a substituent, and a saturated or unsaturated aliphatic which may have a substituent. A hydrocarbon group, an alicyclic hydrocarbon group, or a heteromonocyclic or heteropolycyclic group which may have a substituent, and R ² is independently a hydrogen atom, a halogen atom, a carboxyl group Group, amino group, amide group, hydroxyl group, alkoxy group or allyloxy group, or when n is 2 or more, they may be bonded to each other to form a tetraethylene group or a 1,3-butenyl group. , X ⁻ represents a halogen anion, a borate anion, a phosphate anion, a sulfonate anion or a carboxylate anion, m represents 0 to 5 and n represents 0 to 5). To a ketone compound having an aromatic salt, a general formula (B)

(Wherein R ³ and R ⁴ are each independently an aromatic monocyclic or aromatic polycyclic hydrocarbon group which may have a substituent, saturated or optionally having a substituent, or An unsaturated aliphatic hydrocarbon group or an alicyclic hydrocarbon group, or a heteromonocyclic or heteropolycyclic group which may have a substituent, wherein R ³ and R ⁴ are bonded to each other to form a ring; R ⁵ represents a hydrogen atom or an alkyl group which may have a substituent, and R ⁶ may have an alkyl group or a substituent which may have a substituent. A good aromatic monocyclic or aromatic polycyclic hydrocarbon group, a saturated or unsaturated aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and * represents an asymmetric carbon atom). Obtained by reacting an active nitrogen-containing compound and a Group VIII metal compound of the periodic table Made by transfer hydrogenation asymmetric reduction asymmetric metal complex and hydrogen donor, the general formula (C) and / or formula (D)

(In the formula, R ¹ , R ² , m and n are the same as described above.)
A process for producing an optically active alcohol having a nitrogen-containing heterocycle represented by the formula: The method for producing an optically active alcohol having a nitrogen-containing heterocycle according to claim 1, wherein m and n are 1 and R ² is substituted at the 4-position of the nitrogen-containing heterocycle. The optically active alcohol having a nitrogen-containing heterocycle according to claim 1 or 2, wherein R ¹ is a phenyl group which may have a substituent and R ² is a dihydropyridazyl group which may have a substituent. Manufacturing method. The method for producing an optically active alcohol having a nitrogen-containing heterocycle according to any one of claims 1 to 3, wherein R ¹ is a 4-cyanophenyl group and R ² is a 4-oxodihydropyridazyl group.
In the optically active nitrogen-containing compound represented by the general formula (B), R ³ is

R ⁴ is

R ⁶ is

(Wherein R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom or an alkoxy group having 1 to 8 carbon atoms; o, p, q; Each independently represents 1 to 5.) The method for producing an optically active alcohol having a nitrogen-containing heterocycle according to any one of claims 1 to 4, wherein In the optically active nitrogen-containing compound represented by the general formula (B), R ³ and R ⁴ are bonded to each other,

The method for producing an optically active alcohol having a nitrogen-containing heterocycle according to any one of claims 1 to 5, wherein R ⁸ and p are the same as defined above.   The method for producing an optically active alcohol having a nitrogen-containing heterocycle according to any one of claims 1 to 6, wherein the Group VIII metal compound of the periodic table is a ruthenium compound.   The method for producing an optically active alcohol having a nitrogen-containing heterocycle according to any one of claims 1 to 7, wherein the hydrogen donor is formic acid, formate, or an alcohol compound.   A method for producing an optically active alcohol having a nitrogen-containing heterocycle, wherein one or more bases selected from the group consisting of organic amines, alkali metal hydroxides and alkali metal alkoxides are used. The said manufacturing method in any one of claim | item 1 -8.