JPH11322734A - Ruthenium-optically active phosphine complex, its production, and production of optically active 4-methyl-2-oxetanone by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new complex having a high catalytic activity, and useful as a catalyst capable of providing a high asymmetric yield in an asymmetric reaction, i.e., capable of providing a product having a high optical purity. SOLUTION: This new complex is the one of formula I [L is an optically active phosphine bidentate; T<1> is a carboxylate anion; T2 is a halogen or a carboxylate anion; (n) is 0 or 1; (m) is 1-3; (p) is 0-1; (q) is 1, or when (m) is 2, (q) is 1-1.5]. The complex is obtained, for example, by reacting a ruthenium- optically active phosphine complex of formula II (arene is a hydrocarbon having a benzene ring) with carboxylic acid salts of the formula (T<1> )aZ<1> (Z<1> is an alkali metal or the like; when Z<1> is the alkali metal, (a) is 1, or the like) or salts of the formula Z<2> b(T<2> )c (Z<2> is an alkali metal or mono- or dications; T<2> is a halogen, mono- or dianions; (b) and (c) and each 1 when Z<2> is monocations and T<2> is monoanion, or the like) in a polar solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel ruthenium-iodine-optically active phosphine complex, a method for producing the same, and a method for producing optically active 4-methyl-2-oxetanone using the same. Various organic synthesis reactions,
In particular, the above-mentioned complex used as a catalyst for an asymmetric hydrogenation reaction or the like, a method for producing the same, and an optically active compound 4 which is useful as an intermediate in the organic synthetic chemistry industry such as a polymer raw material, a pharmaceutical synthesis raw material, or a liquid crystal material. The present invention relates to a method for producing methyl-2-oxetanone.

[0002]

2. Description of the Related Art Conventionally, many transition metal complexes have been used as catalysts for organic synthesis reactions. In particular, metal complexes of ruthenium metal and an optically active tertiary phosphine are well known as catalysts for asymmetric hydrogenation reactions.
As a ruthenium-optically active phosphine complex having an optically active tertiary phosphine as a ligand such as 2'-bis (diphenylphosphino) -1,1'-binaphthyl (hereinafter abbreviated as BINAP), Something like that is known.

Ru _x H _y Cl ₂ (tertiary phosphine) ₂ (A) _p (where A represents a tertiary amine, and when y is 0, x is 2, z is 4, and p is 1 Where y is 1, x is 1, z
Is 1 and p is 0) (Japanese Patent Publication No. 4-81596,
JP-B-5-12354).

[R _u H _r (tertiary phosphine) _x ] T _y (where T represents ClO ₄ , BF ₄ , PF ₆ and r is 0
, X represents 1 and y represents 2. When r is 1, x represents 2 and y represents 1. (Japanese Patent Publication Nos. 5-12353 and 5-12355).

[RuX _a (Q) _b (tertiary phosphine)] Y _c } wherein X represents a halogen atom, Q represents benzene or acetonitrile which may have a substituent, and Y represents halogen Atoms, ClO ₄ , PF ₆ , BPh ₄ (where P
h represents a phenyl group. The same applies hereinafter) or BF _4, and when Q is benzene which may have a substituent,
a, b and c each represent 1, and when Q is acetonitrile, when a is 0, b represents 4, c represents 2, and a represents 1
In the case, b represents 2 and c represents 1. When Q is p-cymene among benzenes having a substituent and X and Y are iodine atoms, a, b and c are all 1, a is 1, b is 1, c May be 3 (JP-B-7-57758, JP-A-5-1111639).

(Tertiary phosphine) _w Ru (OCO
R ′) (OCOR ″) wherein R ′ and R ″ are a lower alkyl group, a halogenated lower alkyl group, a phenyl group optionally having a lower alkyl substituent, an α-aminoalkyl group or an α-aminophenyl Represents an alkyl group, or R 'and R "together form an alkylene group, and w represents 1 or 2)
(JP-B-5-11119, JP-B-5-12355)
No.).

RuJ ₂ (tertiary phosphine) (wherein J represents a chlorine atom, a bromine atom or an iodine atom) (R. Noyori et al., J. Am. Chem. Soc., Vol. 109,
No. 19, pp. 5856-5859 (1987)) RuG ₂ (tertiary phosphine) (wherein G represents an allyl group or a methallyl group) (J.
P. Genet et al., Tetrahedron: Asymmetry, Vol. 2, N
o. 7, pp. 555-567 (1991)) However, even if these ruthenium-optically active phosphine complexes are used, their catalytic activity and asymmetric yield are insufficient depending on the target reaction or reaction substrate. There were cases where there was a problem in actual industrialization.

On the other hand, 4-methyl-2-oxetanone (also referred to as “β-butyrolactone” or “β-methyl-β-propiolactone”) has been conventionally used as a polymer raw material, but in recent years, And JP-A-6-2
As described in JP-A-56482, JP-A-6-329768, JP-A-7-53694, JP-A-8-53540 and JP-A-8-127645, the optically active substance is particularly useful. Is attracting attention.

As a method for producing optically active 4-methyl-2-oxetanone, the following method has been reported. (A) 3-obtained by adding hydrobromic acid to crotonic acid
A method in which bromobutyric acid is optically resolved using optically active naphthylethylamine and then cyclized (J. Reid Shelton
et al .; Polymer Letters, Vol. 9, pp. 173-178 (197
1) and T. Satoetal; Tetrahedron Lett., Vol. 21, p.
p. 3377-3380 (1980)).

(B) Reaction of optically active 3-hydroxybutyric acid with triethylorthoacetic acid to obtain optically active 2-ethoxy-2,6-dimethyl-1,3-dioxan-4-one, which is thermally decomposed (A. Griesbeck et al .; H
elv. Chim. Acta, Vol. 70, pp. 1320-1325 (1987) and
R. Breitschuh et al .; Chimia, Vol. 44, pp. 216-218
(1990)).

(C) A method of reacting an optically active 3-hydroxybutyrate with methanesulfonyl chloride to mesylate the hydroxyl group, hydrolyzing the obtained ester, and then condensing and cyclizing with sodium hydrogen carbonate (Y . Zhang e
t al .; Macromolecules, Vol.23, pp. 3206-3212 (199
0)).

Further, as an example using the above-mentioned ruthenium-optically active phosphine complex, the following method has also been reported (d) 4-methylene-2-oxetanone ("diketene").
) In an aprotic solvent such as methylene chloride or tetrahydrofuran [RuCl [(S)-
Or (R) -BINAP (benzene)] Cl, or Ru ₂ Cl4 [(S)-or (R) -BINA
P] ₂ (NEt ₃ ) [where Et represents an ethyl group]
Asymmetric hydrogenation using thiol as a catalyst (T. Ohta et al .; J.
Chem. Soc., Chem. Commun., 1725 (1992)).

However, each of these methods has the following problems. In other words, the method (a) requires a special optically active amine as an optical resolving agent in an equimolar amount with the raw material compound, and an unnecessary enantiomer is by-produced in an equimolar amount with the target compound, so that the method is wasteful and economical. Not an advantageous method. Further, in the methods (b) and (c), it is not easy to synthesize optically active 3-hydroxybutyric acid or an ester thereof as a raw material compound. That is, it is necessary to thermally decompose the optically active poly-3-hydroxybutyrate produced by the microorganism, or to conduct asymmetric reduction after introducing 4-methylene-2-oxetanone into acetoacetate by an alcoholysis reaction. There are many steps and the operation is complicated. The method (d) solves many of the problems of the methods (a) to (c) described above, but still has some problems. That is, the catalyst activity is low and the reaction time is long. Further, the optical purity of the obtained product is 70.
~ 92% e.e. Furthermore, JP-A-6-128245
This method has been improved as reported in Japanese Unexamined Patent Application, First Publication No. Hei 7-182801, Japanese Unexamined Patent Application Publication No. 7-206885, but since the catalytic activity is still low, it is industrially satisfactory. It was not the way to go.

[0014]

Accordingly, an object of the present invention is to provide a catalyst having a high catalytic activity and a high asymmetric yield in an asymmetric reaction, that is, a catalyst capable of obtaining a product having a high optical purity. It is still another object of the present invention to provide a method for producing optically active 4-methyl-2-oxetanone useful as a polymer material or the like in a short time, efficiently and with high optical purity using the catalyst.

[0015]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a novel ruthenium-iodide obtained by a relatively simple method.
The optically active phosphine complex has extremely high catalytic activity,
It can be widely used as an asymmetric synthesis catalyst. In particular, if this is used as a catalyst for the asymmetric hydrogenation of 4-methylene-2-oxetanone, optically active 4-methyl with high optical purity can be efficiently prepared in a short time. It has been found that -2-oxetanone can be produced, and the present invention has been completed.

That is, the present invention relates to formula (1)

Embedded image [Ru- (I) _q- (T ¹ ) _n (L)] _m (T ² ) _p (1) (where L is an optically active bidentate phosphine ligand, T ¹ Represents a carboxylate anion, T ² represents an anion other than a halogen atom and a carboxylate anion, n is from 0 to 1, m is from 1 to 3, p is from 0 to 1, and q is 1 or 1 when m is 2 or 1 The compound is a ruthenium-iodo optically active phosphine complex represented by the following formula:

Further, the present invention provides a compound of the formula (3) [RuI (arene) (L)] I (3) wherein arene is a hydrocarbon having a benzene ring, L
Represents the above-mentioned optically active bidentate phosphine ligand) and a ruthenium-optically active phosphine complex represented by the following formula (4) (T ¹ ) aZ ¹ ... (4) (where Z ¹ is an alkali metal , A represents an alkaline earth metal, a represents ¹ when Z ¹ is an alkali metal, 2 represents Z ^{1 when it} is an alkaline earth metal, and T ¹ is the same as defined in the above formula (1)) Salt or formula (5) Z ² b (T ² ) c (5) (wherein, Z ² represents a mono- or dication such as an alkali metal, an alkaline earth metal, or ammonium, and T ² represents a halogen atom represents mono- or dianion compound excluding carboxylic acids, b and c, if T ² is a mono-anions when Z ² is a mono-cations is 1, T ² when Z ² is mono cations When b is a dianion, b is 2
And c is 1; b and c are 1 when Z ² is a dication and T ² is a dianion; and when Z ² is a dication and T ² is a monoanion. b
Is 1 and c is 2). This is a method for producing the above-mentioned ruthenium-iodo optically active phosphine complex in which a salt represented by the following formula is reacted in a polar solvent.

Further, the present invention provides a compound of the formula (1) [RuI ₂ (arene)] ₂ (6) (where arene represents a hydrocarbon having a benzene ring) and the above formula (1) Table in) the same definition of the optically active bidentate phosphine ligand of the formula and ^{(4) (T 1) aZ} 1 ··· (4) ( wherein, Z ^1, a, T ¹ is the same as previously defined) Or a salt represented by formula (5) Z ² b (T ² ) c (5) (wherein Z ² , b, T ² , and c are the same as defined above). This is a method for producing a ruthenium-iodo optically active phosphine complex represented by the above formula (1) by reacting in a polar solvent.

Further, the present invention relates to the above-mentioned ruthenium-yo-
This is a method for producing optically active 4-methyl-2-oxetanone by asymmetric hydrogenation of 4-methylene-2-oxetanone using a de-optically active phosphine complex as a catalyst.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The ruthenium-iodo optically active phosphine complex of the present invention (hereinafter referred to as [Ru- (I) _q-
(T ¹ ) _n (L)] _m (T ² ) _p is given by the formula (3) [RuI
(Arene) (L)] I-Ruthenium-optically active phosphine complex is reacted with a formula (4) (T ¹ ) aZ ¹ carboxylate or a formula (5) Z ² b (T ² ) c salt in a polar solvent. Or a compound of the formula (6) [RuI ₂ (arene
A) reacting a ruthenium complex of _2, an optically active bidentate phosphine ligand with a salt of formula (4) (T ¹ ) aZ ¹ carboxylate or a salt of formula (5) Z ² b (T ² ) c in a polar solvent; It can be manufactured by two kinds of manufacturing methods.

That is, the above-mentioned ruthenium complex [RuI (aren) was placed in a reaction vessel replaced with an inert gas such as nitrogen.
e) (L)] I (formula (3)) and carboxylate (T ¹ )
aZ ¹ (formula (4)) or a salt Z ² b (T ² ) c (formula (5)) is heated and stirred in a polar solvent to remove the polar solvent, and further, methylene chloride-water is added. It can be obtained by stirring and washing at room temperature in a layer solvent, and the above-mentioned ruthenium complex [RuI (arene) (L)]
I (formula (3)) is heated and stirred in a polar solvent to carry out a stirring reaction to distill off the polar solvent to obtain an intermediate. Further, carboxylate (T ¹ ) aZ ¹ (Formula (4)) or a salt Z ² b (T ² ) c (Formula (5)), and the mixture can be stirred at room temperature to react.

The above ruthenium complex [RuI
₂ (arene)] ₂ of the formula (6) and bidentate phosphine ligand (L) and carboxylic acid salts (T ¹⁾ aZ ¹ (formula (4))
Alternatively, the salt Z ² b (T ² ) c (formula (5)) is heated and stirred in a polar solvent to cause a reaction by stirring to distill off the polar solvent, and further stirred at room temperature in a two-layer solvent of methylene chloride-water. In addition, the ruthenium complex [RuI ₂ (arene)] ₂ (6) and the bidentate phosphine ligand (L) are heated and stirred in a polar solvent to react with the polar solvent. Is distilled off to obtain an intermediate, and the carboxylate (T ¹ ) aZ ¹ (formula (4)) or the salt Z ² b (T ² ) c (formula (5) )), And react by stirring at room temperature.

[Ru- (I) _q- (T ¹ )]
_{n (L)] m (T} 2) which is a raw material for the production of _p,
Ruthenium-optically active phosphine complex [RuI (arene
) (L)] I (in formula (3)), the optically active bidentate phosphine ligand represented by L is represented by formula (2)

Embedded image (Hereinafter, it may be referred to as BIPH. In the formula, R ¹ represents a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a lower alkylamino group having 1 to 4 carbon atoms, and a halogen atom. which may have a substituent selected from the group consisting ant - group or a cycloalkyl group having a carbon number of 3 to 8, R ² and R ³ are each the same or different and may a hydrogen atom, a halogen atom, a carbon number 1 To 4 lower alkyl groups, lower alkoxy groups having 1 to 4 carbon atoms, or R ² and R ³
Represents a group which may form a 5- or 6-membered ring together).

In the formula (2), BIPH is represented by R
BIPHEP when ¹ is a phenyl group, R ² is a hydrogen atom, and R ³ is a methyl group (described below (nu)); BICHE when R ¹ is a cyclohexyl group, R ² is a hydrogen atom, and R ³ is a methyl group
P (described later), R ¹ is a phenyl group, R ² is a hydrogen atom, and when R ³ is a methoxy group, MBIPHEP (described later (No.)), R ¹ is a cyclohexyl group, R ² is a hydrogen atom,
MBICEP when R ³ is a methoxy group (described later (c))
Can be mentioned.

Such optically active biphenyl tertiary phosphines include, in addition to BIPHEP and the like, a compound represented by the formula (7)

Embedded image (Hereinafter sometimes referred to as R ¹ -BINAP, where R
¹ is a lower alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
A lower alkoxy group, a lower alkylamino group having 1 to 4 carbon atoms and an aryl group which may have a substituent selected from the group consisting of halogen atoms or a cycloalkyl group having 3 to 8 carbon atoms). An optically active tertiary phosphine represented by the formula (8)

[0026]

Embedded image (Hereinafter,. In formula which may be referred to as H ⁸ -R ¹ -BINAP, R ¹ is the same definition as above for R ¹ over BINAP)
And an optically active tertiary phosphine of the formula (9)

Embedded image (Hereinafter, R ¹ has the same definition as the above R ¹ -BINAP).

The aryl group represented by R ¹ in R ¹ -BINAP (formula (7)) includes phenyl, 2-naphthyl, p-substituted phenyl, m-substituted phenyl,
Examples include a phenyl group having a substituent such as an m-diphenyl group, and a 2-naphthyl group having a substituent such as a 6-substituted-2-naphthyl group. The substituents that may be substituted on the phenyl group and the naphthyl group include a methyl group, t
a lower alkyl group such as an tert-butyl group ("lower" means a straight or branched chain having 1 to 4 units; the same applies hereinafter), a lower alkoxy group, a lower alkylamine group, and a halogen atom such as a chlorine atom Can be mentioned. Further, a cycloalkyl group having 3 to 8 carbon atoms represented by R ¹ is particularly preferably a cyclopentyl group or a cyclohexyl group.

Specific examples represented by R ¹ -BINAP include the following. Although any of the tertiary phosphines has an (R) -form and an (S) -form, the notation is omitted. same as below.

(A) 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl (hereinafter simply referred to as "BINA"
P). (A) 2,2'-bis (di-p-tolylphosphino)-
1,1′-binaphthyl (hereinafter abbreviated as “T-BINAP”) (c) 2,2′-bis [di- (p-tert-butylphenyl) phosphino] -1,1′-binaphthyl
(Abbreviated as "tBu-BINAP") (d) 2,2'-bis (di-m-tolylphosphino)-
1,1′-binaphthyl (hereinafter “m-T-BINAP”
(E) 2,2'-bis [di- (3,5-dimethylphenyl) phosphino] -1,1'-binaphthyl (hereinafter referred to as "D
M-BINAP) (f) 2,2'-bis [di- (3,5-di-tert-
[Butylphenyl) phosphino] -1,1′-binaphthyl (hereinafter abbreviated as “DtBu-BINAP”) (g) 2,2′-bis [di- (p-methoxyphenyl)
Phosphino] -1,1′-binaphthyl (hereinafter referred to as “MeO
-BINAP). (H) 2,2'-bis [di- (p-chlorophenyl) phosphino] -1,1'-binaphthyl (hereinafter, "p-Cl
-BINAP). (G) 2,2'-bis (di-2-naphthylphosphino)
-1,1'-binaphthyl (hereinafter "Naph-BINA"
Abbreviated as "P") (co) 2,2'-bis (dicyclopentylphosphino)
-1,1'-binaphthyl (hereinafter abbreviated as "cpBINAP") (sa) 2,2'-bis (dicyclohexylphosphino)
-1,1'-binaphthyl (hereinafter abbreviated as "CyBINAP")

These tertiary phosphines are disclosed in
JP-A-81596, JP-B-7-33392, JP-B-7-68260, JP-A-1-68386 or JP-A-4-74192, JP-A-9-124
It can be prepared by the method described in US Pat.

Ruthenium-optically active phosphine complex [R
uI (arene) (L)] I (formula (3)) is a ruthenium-optically active phosphine complex represented by JP-B-7-577.
No. 58 and JP-A-5-1111639. Specific examples of the thus obtained ruthenium-optically active phosphine complex represented by the above formula (3) include the following.

[RuI (benzene) (BINAP)] I [RuI (benzene) (T-BINAP)] I [RuI (benzene) (tBu-BINAP)] I [RuI (benzene) (m-T-BINAP)] I [RuI (benzene) (DM-BINAP)] I [RuI (benzene) (DtBu-BINAP)] I [RuI (benzene) (MeO-BINAP)] I [RuI (benzene) (p-Cl-BINAP)] I [RuI (benzene) (Naph-BINAP)] I [RuI (benzene) (cpBINAP)] I [RuI (benzene) (CyBINAP)] I [RuI (p-cymene) (BINAP)] I [RuI (p- cymene) (T-BINAP)] I [RuI (p-cymene) (tBu-BINAP)] I [RuI (p-cymene) (m-T-BINAP)] I [RuI (p-cymene) (DM-BINAP)] I [RuI (p-cymene) (DtBu-BINAP)] I [RuI (p-cymene) (MeO-BINAP)] I [RuI (p-cymene) (p-Cl-BINAP)] I [RuI (p-cymene) (Naph-BINAP)] I [RuI (p-cymene) (cpBINAP)] I [RuI (p-cymene) (CyBINAP)] I

2,2'-bis (diphenylphosphino) -1, represented by H ⁸ -R ¹ -BINAP of the formula (8)
For 1'-octahydrobinaphthyl, the above R ¹ -B
Compounds similar to INAP can be shown.

The R ¹ -SEGPHOSs are disclosed in Japanese Patent Application ^No. Hei 8-3
It is obtained in 5 steps from 3,4-methylenedioxybenzene according to the method described in 11211. Specific examples of the tertiary phosphine include the following.
Although any of the tertiary phosphines has an (R) -form and an (S) -form, the notation is omitted. same as below.

(S) [(5,6), (5 ', 6')-bis (methylenedioxy) biphenyl-2,2'-diyl] bis (diphenylphosphine) (hereinafter simply referred to as "SE
GPHSOS). (S) [(5,6), (5 ', 6')-bis (methylenedioxy) biphenyl-2,2'-diyl] bis (di-
p-tolylphosphine) (hereinafter referred to as “T-SEGPHO”
S) [(5), (5 ', 6')-bis (methylenedioxy) biphenyl-2,2'-diyl] bis [di-
(P-tert-butylphenyl) phosphine] (hereinafter abbreviated as “tBu-SEGPHOS”) (so) [(5,6), (5 ′, 6 ′)-bis (methylenedioxy) biphenyl-2, 2'-diyl] bis (di-
m-tolyl-phosphine) (hereinafter referred to as "m-T-SEGP"
(Abbreviated as HOS)) (t) [(5,6), (5 ', 6')-bis (methylenedioxy) biphenyl-2,2'-diyl] bis [di-
(3,5-dimethylphenyl) phosphine] (hereinafter, referred to as
(H) [(5), (5 ', 6')-bis (methylenedioxy) biphenyl-2,2'-diyl] bis [di-
(3,5-di-tert-butylphenyl) phosphine] (hereinafter abbreviated as “DtBu-SEGPHOS”) (T) [(5,6), (5 ′, 6 ′)-bis (methylenedioxy) Biphenyl-2,2'-diyl] bis [di-
(P-methoxyphenyl) phosphine] (hereinafter, “Me
O-SEGPHOS) (T) [(5,6), (5 ', 6')-bis (methylenedioxy) biphenyl-2,2'-diyl] bis [di-
(P-chlorophenyl) phosphine] (hereinafter, “p-C
(g). (g) [(5,6), (5 ′, 6 ′)-bis (methylenedioxy) biphenyl-2,2′-diyl] bis (di-
2-naphthylphosphine) (hereinafter, “Naph-SEG”
(NA) [(5,6), (5 ′, 6 ′)-bis (methylenedioxy) biphenyl-2,2′-diyl] bis (dicyclopentylphosphine) (hereinafter “cpSEGPHO”)
(D) [(5,6), (5 ', 6')-bis (methylenedioxy) biphenyl-2,2'-diyl] bis (dicyclohexylphosphine) (hereinafter referred to as "CYSEGPHO").
S ”)

(Nu) [bis (6,6'-dimethylbiphenyl-2,2 '-] (diphenylphosphine) (hereinafter referred to as
(Abbreviated as "BIPHEP") (d) [bis (6,6'-dimethylbiphenyl-2,
2 ′-] (Dicyclohexylphosphine) (hereinafter referred to as “B
(Abbreviated as "ICHEP") (no) [bis (6,6'-dimethoxybiphenyl-2,
2'-] (diphenylphosphine) (hereinafter referred to as [MBIP
Abbreviated as "HEP") (c) [bis (6,6'-dimethoxybiphenyl-2,
2 '-] (dicyclohexylphosphine) (hereinafter referred to as [M
BICHEP ”)

In the present invention, L is R ¹ -SEGPHO.
The ruthenium-optically active phosphine complex represented by S [RuI (arene) (L)] I (3) is disclosed in
It can be obtained by the methods described in JP-A-1289 and JP-A-5-11639. Specific examples of the thus obtained ruthenium-optically active phosphine complex obtained by the above formula (3) include the following.

[RuI (benzene) (SEGPHO)
S)] I [RuI (benzene) (T-SEGPHOS)] I [RuI (benzene) (tBu-SEGPHOS)] I [RuI (benzene) (m-T-SEGPHOS)] I [RuI (benzene) (DM- SEPGHOS)] I [RuI (benzene) (DtBu-SEGPHOS)]
I [RuI (benzene) (MeO-SEGPHOS)] I [RuI (benzene) (p-Cl-SEGPHOS)]
I [RuI (benzene) (Naph-SEGPHOS)]
I [RuI (benzene) (cpSEGPHOS)] I [RuI (benzene) (CySEGPHOS)] I [RuI (p-cymene) (SEGPHOS)] I [RuI (p-cymene) (T-SEGPHOS)] I [RuI ( p-cymene) (tBu-SEGPHOS)]
I [RuI (p-cymene) (m-T-SEGPHOS)]
I [Rul (p-cymene) (DM-SEGPHOS)] I [Rul (p-cymene) (DtBu-SEGPHO)
S)] I [RuI (p-cymene) (MeO-SEGPHOS)]
I [RuI (p-cymene) (p-Cl-SEGPHO)
S)] I [RuI (p-cymene) (Naph-SEGPHO)
S)] I [Rul (p-cymene) (cpSEGPHOS)] I [Rul (p-cymene) (CySEGPHOS)] I

BIPHEP, BICHEP, MBIPH
EP and MBICHEP also include compounds similar to SEGPHOS.

The above ruthenium complex [RuI ₂ (arene)
The ruthenium-iodide complex represented by ₂ ) (6)
For example, Zelonka (RA Zelonka et al .; Can. J.
Chem., Vol 50, 3063 (1972)). Specific examples of the obtained ruthenium-optically active phosphine complex include the following. [Ru ₂ (benzene)] ₂ [Ru ₂ (p-cymene)] ₂

On the other hand, the production method of the ruthenium-iodo-optically active bidentate phosphine complex represented by the formula (1) of the present invention is based on the ruthenium-optically active compound represented by the formula (3) [RuI (arene) (L)] I. Phosphine complex and formula (4) (T ¹ )
a carboxylate represented by aZ ¹ or Z ² b represented by the formula (5):
It is prepared by reacting a salt represented by (T ² ) c in a polar solvent, or prepared by reacting a salt represented by the formula (6) [RuI ₂ (arene)]
Ruthenium complex represented by ₂ and phosphine ligand (L)
Is reacted in a polar solvent, and the compound of the formula (4) (T ¹ ) aZ
It can be produced by reacting ¹ or a salt represented by the formula (5) Z ² b (T ² ) c.

Examples of the carboxylate represented by the formula (4) include lithium formate, lithium acetate, lithium propionate, lithium butyrate, lithium pyruvate, and the like.
Lithium benzoate, lithium trifluoroacetate, sodium formate, sodium acetate, sodium propionate,
Sodium butyrate, sodium pyruvate, sodium benzoate, sodium trifluoroacetate, potassium formate,
Potassium acetate, potassium propionate, potassium butyrate,
Alkali metal carboxylate, such as potassium pyruvate, potassium benzoate, potassium trifluoroacetate,
Alkaline earth metal carboxylates such as calcium formate, calcium acetate, calcium propionate, calcium butyrate, calcium pyruvate, calcium benzoate, calcium trifluoroacetate, silver formate, silver acetate, silver propionate, silver butyrate, Other carboxylate salts such as silver pyruvate, silver benzoate and silver trifluoroacetate can be mentioned, and sodium acetate and sodium trifluoroacetate are particularly preferable.

On the other hand, as the salts represented by the above formula (5), for example, sodium methanesulfonate (sodium mesylate) (hereinafter abbreviated as “NaOMs”), methanesulfonate (sodium Tosylates)
(Hereinafter abbreviated as "NaOTs"), lithium trifluoromethanesulfonate (lithium triflate)
(Hereinafter abbreviated as “LiOTf”), potassium nonafluorobutane sulfonate (hereinafter “KOS (O) ₂
C ₄ F ₉ ), NaOTf, Mg (OTf)
_{2, AgOTf, NH 4 OTf,} LiBF 4, NaBF
_{4, KBF 4, AgBF 4,} Ca (BF 4) 2, NH 4
BF ₄ , LiPF ₆ , NaPF ₆ , KPF ₆ , AgPF
₆ , Ca (PF ₆ ) ₂ , NH ₄ PF ₆ , LiClO ₄ ,
NaClO ₄ , KClO ₄ , AgClO ₄ , Ca (Cl
O ₄ ) ₂ , NH ₄ ClO ₄ , LiBPh ₄ , NaBPh
₄ , KBPh ₄ , AgBPh ₄ , Ca (BPh ₄ ) ₂ ,
NH ₄ BPh ₄ , Na ₂ SO ₄ , K ₂ SO ₄ , MgSO
₄ , CaSO ₄ , (NH ₄ ) ₂ SO ₄ , Na ₂ CO ₃ ,
K ₂ CO ₃ , MgCO ₃ , CaCO ₃ , (NH4) ₂ C
O ₃ , potassium heptadecafluorooctane sulfone
(Hereinafter abbreviated as “KOS (O) ₂ C ₈ F ₁₇ ”) and the like, particularly NaOTf, NaPF ₆ , NH ₄
PF ₆ , NaClO ₄ , NH ₄ ClO ₄ , KOS (O)
₂ C ₄ F ₉ and KOS (O) ₂ C ₈ F ₁₇ are preferred.

The amount of the formula (4) (T ¹ ) aZ ¹ carboxylate or the formula (5) Z ² b (T ² ) c salt used is determined by the formula (3) [RuI (arene) (L)] I Ruthenium-optically active phosphine complex or formula (6) [RuI ₂ (arene
)] The amount is preferably in the range of about 0.5 to 5 moles per mole of ₂ ruthenium complex, and particularly preferably about 1 to 4 moles.
The molar ratio is preferably in the range of 2 times.

Examples of the polar solvent used in the reaction include lower alcohols such as methanol and ethanol, dimethylformamide, dimethylsulfoxide, dioxane, and the like.
Examples thereof include tetrahydrofuran and a mixed solvent of methanol and methylene chloride. Formula (1) of the present invention [Ru- (I) _{q
^{- (T 1) n (L}} )] m (T 2) p ruthenium - iodo - temperature to produce the optically active bidentate phosphine complex in the case of formula ^{(4) (T 1) aZ} 1 -carboxylic acid salts About 4
0 Further to 60 ° C., preferably from 50 to 55 ° C., or Formula ^{(5) Z 2 b (T} 2) in the case of c salts about 60 to 9
The temperature is 0 ° C., preferably 70 to 80 ° C., and the reaction time is about 10 to 40 hours, preferably about 15 to 20 hours. After the reaction, remove the hydrophobic organic solvent layer,
It is obtained by purification by a method such as evaporation of the solvent and drying.

The desired formula (1) of the present invention [Ru-
(I) The ruthenium-iodo-optically active bidentate phosphine complex represented by _q- (T ¹ ) _n (L)] _m (T ² ) _p is
A ruthenium-optically active phosphine complex represented by the formula (3) [RuI (arene) (L)] I and (T ¹ ) of the formula (4)
a has a structure in which an arene molecule of a complex is eliminated by reacting a Z ¹ carboxylate or a salt of the formula (5) Z ² b (T ² ), or a compound of the formula (6) [RuI ₂ (arene)] _The ruthenium complex represented by formula ( ² ) is reacted with an optically active bidentate phosphine and a salt of formula (4) (T ¹ ) a Z ¹ carboxylate or a salt of formula (5) Z ² b (T ² ) in the same manner as described above.
ene has a detached structure. In the case of a carboxylate, it is a complex having a structure in which an iodine atom is substituted with a carboxyl group. That is, it is a compound comprising ruthenium, iodine, a carboxyl group or a T ² group of a salt and an optically active tertiary phosphine which are the minimum constituents of the complex of the present invention. −
(I) _q- (T ¹ ) _n (L)] _m (T ² ) _p .

The ruthenium represented by the formula (1) of the present invention
Representative compounds of the iodine-optically active bidentate phosphine complex include the following compounds. In addition,
Although the absolute configuration of the complex of the present invention can be obtained depending on the absolute configuration (R) or (S) of the phosphine used, their representation is omitted.

[Rul (HCOO) (BINAP)] ₂ [Rul (HCOO) (T-BINAP)] ₂ [Rul (CH ₃ COO) (BINAP)] ₂ [Rul (CH ₃ COO) (T-BINAP)] ₂ [RuI (CH ₃ COO) (tBu-BINAP)] ₂ [RuI (CH ₃ COO) (m-T-BINAP)] ₂ [RuI (CH ₃ COO) (DM-BINAP)] ₂ [RuI (CH ₃ COO) (DtBu-BINAP)]
₂ [RuI (CH ₃ COO) (MeO-BINAP)] ₂ [RuI (CH ₃ COO) (p-Cl-BINAP)]
₂ [RuI (CH ₃ COO) (Naph-BINAP)]
₂ [RuI (CH ₃ COO) (cpBINAP)] ₂ [RuI (CH ₃ COO) (CyBINAP)] ₂ [RuI (CH ₃ CH ₂ COO) (BINAP)] ₂ [RuI (CH ₃ CH ₂ COO) (T -BINAP)]
₂ [RuI (CH ₃ CH ₂ CH ₂ COO) (BINA
P)] ₂ [RuI (CH ₃ CH ₂ CH ₂ COO) (T-BINA)
P)] ₂ [RuI (CH ₃ COOO) (BINAP)] ₂ [RuI (CH ₃ COOO) (T-BINAP)] ₂ [RuI (PhCOO) (BINAP)] ₂ [RuI (PhCOO) (T-BINAP) ] ₂ [RuI (CF ₃ COO) (BINAP)] ₂ [RuI (CF ₃ COO) (T-BINAP)] ₂

[Ru-I- (BINAP)] (OMs) [Ru-I- (BINAP)] (OTs) [Ru-I- (BINAP)] (OTf) [Ru-I- (BINAP)] @ OS (O) ₂ C
₄ F ₉ ｝ [Ru-I- (BINAP)] (BF ₄ ) [Ru-I- (BINAP)] (PF ₆ ) [Ru-I- (BINAP)] (ClO ₄ ) [Ru-I- (BINAP) )] (BPh ₄ ) [Ru-I- (BINAP)] (SO ₄ ) [Ru-I- (BINAP)] (CO ₃ ) [Ru-I- (T-BINAP)] (OMs) [Ru-I − (T-BINAP)] (OTs) [Ru-I- (T-BINAP)] (OTf) [Ru-I- (T-BINAP)] ｛OS (O) ₂ C ₄
F ₉ ｝ [Ru-I- (T-BINAP)] (BF ₄ ) [Ru-I- (T-BINAP)] (PF ₆ ) [Ru-I- (T-BINAP)] (ClO ₄ ) [Ru -I- (T-BINAP)] ( BPh 4) [Ru-I- (T-BINAP)] (SO 4) [Ru-I- (T-BINAP)] (CO 3)

[Ru-I- (tBu-BINAP)] (OMs) [Ru-I- (tBu-BINAP)] (OTs) [Ru-I- (tBu-BINAP)] (OTf) [Ru-I- (TBu-BINAP)] ｛OS (O) _{2
C 4 F 9} [Ru-} I- (tBu-BINAP)] (BF 4) [Ru-I- (tBu-BINAP)] (PF 6) [Ru-I- (tBu-BINAP)] (ClO 4) [Ru-I- (tBu-BINAP )] (BPh 4) [Ru-I- (tBu-BINAP)] (SO 4) [Ru-I- (tBu-BINAP)] (CO 3) [Ru-I- (M-T-BINAP)] (OMs) [Ru-I- (m-T-BINAP)] (OTs) [Ru-I- (m-T-BINAP)] (OTf) [Ru-I- (m −T-BINAP)] ｛OS (O) ₂
C ₄ F ₉ ｝ [Ru-I- (m-T-BINAP)] (BF ₄ ) [Ru-I- (m-T-BINAP)] (PF ₆ ) [Ru-I- (m-T-BINAP) )] (ClO ₄ ) [Ru-I- (m-T-BINAP)] (BPh ₄ ) [Ru-I- (m-T-BINAP)] (SO ₄ ) [Ru-I- (m-T- (BINAP)] (CO ₃ ) [Ru-I- (DM-BINAP)] (OMs) [Ru-I- (DM-BINAP)] (OTs) [Ru-I- (DM-BINAP)] (OTf) [ Ru-I- (DM-BINAP)] @ OS (O) ₂ C
_{4 F 9} [Ru-I-} (DM-BINAP)] (BF 4) [Ru-I- (DM-BINAP)] (PF 6) [Ru-I- (DM-BINAP)] (ClO 4) [ Ru-I- (DM-BINAP) ] (BPh 4) [Ru-I- (DM-BINAP)] (SO 4) [Ru-I- (DM-BINAP)] (CO 3)

[Ru-I- (DtBu-BINAP)]
(OMs) [Ru-I- (DtBu-BINAP)] (OTs) [Ru-I- (DtBu-BINAP)] (OTf) [Ru-I- (DtBu-BINAP)] @ OS (O)
₂ C ₄ F ₉ ｝ [Ru-I- (DtBu-BINAP)] (BF ₄ ) [Ru-I- (DtBu-BINAP)] (PF ₆ ) [Ru-I- (DtBu-BINAP)] (ClO ₄ ) [Ru-I- (DtBu- BINAP)] (BPh 4) [Ru-I- (DtBu-BINAP)] (SO 4) [Ru-I- (DtBu-BINAP)] (CO 3) [Ru-I -(MeO-BINAP)] (OMs) [Ru-I- (MeO-BINAP)] (OTs) [Ru-I- (MeO-BINAP)] (OTf) [Ru-I- (MeO-BINAP)]} OS (O) _{2
C 4 F 9} [Ru-} I- (MeO-BINAP)] (BF 4) [Ru-I- (MeO-BINAP)] (PF 6) [Ru-I- (MeO-BINAP)] (ClO 4) [Ru-I- (MeO-BINAP)] (BPh ₄ ) [Ru-I- (MeO-BINAP)] (SO ₄ ) [Ru-I- (MeO-BINAP)] (CO ₃ )

[Ru-I- (p-Cl-BINAP)] (OMs) [Ru-I- (p-Cl-BINAP)] (OTs) [Ru-I- (p-Cl-BINAP)] (OTf ) [Ru-I- (p-Cl-BINAP)] @ OS (O)
₂ C ₄ F ₉ ｝ [Ru-I- (p-Cl-BINAP)] (BF ₄ ) [Ru-I- (p-Cl-BINAP)] (PF ₆ ) [Ru-I- (p-Cl- BINAP)] (ClO ₄ ) [Ru-I- (p-Cl-BINAP)] (BPh ₄ ) [Ru-I- (p-Cl-BINAP)] (SO ₄ ) [Ru-I- (p-Cl -BINAP)] (CO ₃ )

[Ru-I- (Naph-BINAP)] (OMs) [Ru-I- (Naph-BINAP)] (OTs) [Ru-I- (Naph-BINAP)] (OTf) [Ru-I- (Naph-BINAP)] @ OS (O)
₂ C ₄ F ₉ ｝ [Ru-I- (Naph-BINAP)] (BF ₄ ) [Ru-I- (Naph-BINAP)] (PF ₆ ) [Ru-I- (Naph-BINAP)] (ClO ₄ ) [Ru-I- (Naph- BINAP)] (BPh 4) [Ru-I- (Naph-BINAP)] (SO 4) [Ru-I- (Naph-BINAP)] (CO 3) [Ru-I - (cpBINAP)] (OMs) [Ru-I- (cpBINAP)] (OTs) [Ru-I- (cpBINAP)] (OTf) [Ru-I- (cpBINAP)] {OS (O) 2 C 4
F ₉ ｝ [Ru-I- (cpBINAP)] (BF ₄ ) [Ru-I- (cpBINAP)] (PF ₆ ) [Ru-I- (cpBINAP)] (ClO ₄ ) [Ru-I- (cpBINAP) ] (BPh ₄ ) [Ru-I- (cpBINAP)] (SO ₄ ) [Ru-I- (cpBINAP)] (CO ₃ )

[Ru-I- (CyBINAP)] (OMs) [Ru-I- (CyBINAP)] (OTs) [Ru-I- (CyBINAP)] (OTf) [Ru-I- (CyBINAP)] @ OS (O) ₂ C ₄
F ₈ ｝ [Ru-I- (CyBINAP)] (BF ₄ ) [Ru-I- (CyBINAP)] (PF ₆ ) [Ru-I- (CyBINAP)] (ClO ₄ ) [Ru-I- (CyBINAP) ] (BPh ₄ ) [Ru-I- (CyBINAP)] (SO ₄ ) [Ru-I- (CyBINAP)] (CO ₃ )

[Ru (I) _1.5 (BINAP)] ₂ (OMs) [Ru (I) _1.5 (BINAP)] ₂ (OTs) [Ru (I) _1.5 (BINAP)] ₂ (OTf) [Ru (I) _{1.5 (BINAP)] 2 {OS} (O) 2 C
₄ F ₉ ｝ [Ru (I) _1.5 (BINAP)] ₂ (BF ₄ ) [Ru (I) _1.5 (BINAP)] ₂ (PF ₆ ) [Ru (I) _1.5 (BINAP)] ₂ (ClO ₄ ) [ Ru (I) _1.5 (BINAP)] ₂ (BPh ₄ ) [Ru (I) _1.5 (T-BINAP)] ₂ (OMs) [Ru (I) _1.5 (T-BINAP)] ₂ (OTs) [Ru (I ) _1.5 (T-BINAP)] ₂ (OTf) [Ru (I) _1.5 (T-BINAP)] ₂ ｛OS (O)
₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (T-BINAP)] ₂ (BF ₄ ) [Ru (I) _1.5 (T-BINAP)] ₂ (PF ₆ ) [Ru (I) _1.5 (T-BINAP) )] ₂ (ClO ₄ ) [Ru (I) _1.5 (T-BINAP)] ₂ (BPh ₄ ) [Ru (I) _1.5 (tBu-BINAP)] ₂ (OM
s) [Ru (I) _1.5 (tBu-BINAP)] ₂ (OT
s) [Ru (I) _1.5 (tBu-BINAP)] ₂ (OTf) [Ru (I) _1.5 (tBu-BINAP)] ₂ ｛OS
(O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (tBu-BINAP)] ₂ (B
F ₄ ) [Ru (I) _1.5 (tBu-BINAP)] ₂ (P
F ₆ ) [Ru (I) _1.5 (tBu-BINAP)] ₂ (ClO
₄ ) [Ru (I) _1.5 (tBu-BINAP)] ₂ (BPh
₄ )

[Ru (I) _1.5 (m-T-BINA)
P)] ₂ (OMs) [Ru (I) _1.5 (m-T-BINAP)] ₂ (OT
s) [Ru (I) _1.5 (m-T-BINAP)] ₂ (OT
f) [Ru (I) _1.5 (m-T-BINAP)] ₂ @ OS
(O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (m-T-BINAP)] ₂ (B
F ₄ ) [Ru (I) _1.5 (m-T-BINAP)] ₂ (P
F ₆ ) [Ru (I) _1.5 (m-T-BINAP)] ₂ (ClO
₄ ) [Ru (I) _1.5 (m-T-BINAP)] ₂ (BPh
₄ ) [Ru (I) _1.5 (DM-BINAP)] ₂ (OMs) [Ru (I) _1.5 (DM-BINAP)] ₂ (OTs) [Ru (I) _1.5 (DM-BINAP)] ₂ (OTf) [Ru (I) _1.5 (DM-BINAP)] ₂ @ OS
(O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (DM-BINAP)] ₂ (BF ₄ ) [Ru (I) _1.5 (DM-BINAP)] ₂ (PF ₆ ) [Ru (I) _1.5 ( DM-BINAP)] ₂ (Cl
O ₄ ) [Ru (I) _1.5 (DM-BINAP)] ₂ (BPh
4) [Ru (I) _1.5 (DtBu-BINAP)] ₂ (OM
s) [Ru (I) _1.5 (DtBu-BINAP)] 2 (OT
s) [Ru (I) _1.5 (DtBu-BINAP)] ₂ (OT
f) [Ru (I) _1.5 (DtBu-BINAP)] ₂ (BF
₄ ) [Ru (I) _1.5 (DtBu-BINAP)] ₂ (PF
₆ ) [Ru (I) _1.5 (DtBu-BINAP)] ₂ (Cl
O ₄ ) [Ru (I) _1.5 (DtBu-BINAP)] ₂ (BP
h ₄₎

[Ru (I) _1.5 (MeO-BINA)
P)] ₂ (OMs) [Ru (I) _1.5 (MeO-BINAP)] ₂ (OT
s) [Ru (I) _1.5 (MeO-BINAP)] ₂ (OT
f) [Ru (I) _1.5 (MeO-BINAP)] ₂ @ OS
(O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (MeO-BINAP)] ₂ (B
F ₄ ) [Ru (I) _1.5 (MeO-BINAP)] ₂ (P
F ₆ ) [Ru (I) _1.5 (MeO-BINAP)] ₂ (ClO
₄ ) [Ru (I) _1.5 (MeO-BINAP)] ₂ (BPh
₄ ) [Ru (I) _1.5 (p-Cl-BINAP)] ₂ (OM
s) [Ru (I) _1.5 (p-Cl-BINAP)] ₂ (OT
s) [Ru (I) _1.5 (p-Cl-BINAP)] ₂ (OT
f) [Ru (I) _1.5 (p-Cl-BINAP)] ₂ @ OS
(O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (p-Cl-BINAP)] ₂ (BF
₄ ) [Ru (I) _1.5 (p-Cl-BINAP)] ₂ (PF
₆ ) [Ru (I) _1.5 (p-Cl-BINAP)] ₂ (Cl
O ₄ ) [Ru (I) _1.5 (p-Cl-BINAP)] ₂ (BP
h ₄₎

[Ru (I) _1.5 (Naph-BINA)
P)] ₂ (OMs) [Ru (I) _1.5 (Naph-BINAP)] ₂ (OT
s) [Ru (I) _1.5 (Naph-BINAP)] ₂ (OT
f) [Ru (I) _1.5 (Naph-BINAP)] ₂ @ OS
(O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (Naph-BINAP)] ₂ (BF
₄ ) [Ru (I) _1.5 (Naph-BINAP)] ₂ (PF
₆ ) [Ru (I) _1.5 (Naph-BINAP)] ₂ (Cl
O ₄ ) [Ru (I) _1.5 (Naph-BINAP)] ₂ (BP
h ₄ ) [Ru (I) _1.5 (cpBINAP)] ₂ (OMs) [Ru (I) _1.5 (cpBINAP)] ₂ (OTs) [Ru (I) _1.5 (cpBINAP)] ₂ (OTf) [Ru (I) _1.5 (cpBINAP)] ₂ @OS (O)
₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (cpBINAP)] ₂ (BF ₄ ) [Ru (I) _1.5 (cpBINAP)] ₂ (PF ₆ ) [Ru (I) _1.5 (cpBINAP)] ₂ (ClO ₄ ) [Ru (I) _1.5 (cpBINAP)] ₂ (BPh ₄ )

[Ru (I) _1.5 (CyBINAP)] ₂
(OMs) [Ru (I) _1.5 (CyBINAP)] ₂ (OTs) [Ru (I) _1.5 (CyBINAP)] ₂ (OTf) [Ru (I) _1.5 (CyBINAP)] ₂ ｛OS (O)
₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (CyBINAP)] ₂ (BF ₄ ) [Ru (I) _1.5 (CyBINAP)] ₂ (PF ₆ ) [Ru (I) _1.5 (CyBINAP)] ₂ (ClO ₄ ) ) [Ru (I) _1.5 (CyBINAP)] ₂ (BPh ₄ ) [Ru (I) _1.5 (BINAP)] ₂ ｛OS (O) ₂ C
₈ F ₁₇ ｝ [Ru (I) _1.5 (T-BINAP)] ₂ ｛OS (O)
₂ C ₈ F ₁₇ ｝ [Ru (I) _1.5 (tBu-BINAP)] ₂ ｛OS
_{(O) 2C 8 F 17}} [Ru (I) 1.5 (m-T-BINAP)] 2 {OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru (I) _1.5 (DM-BINAP)] ₂ ｛OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru (I) _1.5 (DtBu-BINAP)] ₂ ｛OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru (I) _1.5 (MeO-BINAP)] ₂ ｛OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru (I) _1.5 (p-Cl-BINAP)] ₂ ｛OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru (I) _1.5 (cpBINAP)] ₂ ｛OS (O)
₂ C ₈ F ₁₇ ｝ [Ru (I) _1.5 (CyBINAP)] ₂ ｛OS (O)
₂ C ₈ F ₁₇ ｝

[Ru (I) _1.5 (BINAP)] ₂ ｛O
S (O) ₂ (iso-C ₃ F ₇ )｝ [Ru (I) _1.5 (T-BINAP)] ₂ ｛OS (O)
₂ (iso-C ₃ F ₇ )｝ [Ru (I) _1.5 (BINAP)] ₂ ｛OS (O)
₂ (tert-C ₄ F ₉ )｝ [Ru (I) _1.5 (T-BINAP)] ₂ ｛OS (O) ₂
(Tert-C ₄ F ₉ )｝ [Ru (I) _1.5 (BINAP)] ₂ ｛OS (O)
₂ (cyclo-C ₆ F ₁₁ )｝ [Ru (I) _1.5 (T-BINAP)] ₂ ｛OS (O) ₂
(cyclo-C ₆ F ₁₁ )｝

[Ru-I- (SEGPHOS)] (OMs) [Ru-I- (SEGPHOS)] (OTs) [Ru-I- (SEGPHOS)] (OTf) [Ru-I- (SEGPHOS)] ｛OS (O) ₂ C ₄
F ₉ ｝ [Ru-I- (SEGPHOS)] (BF ₄ ) [Ru-I- (SEGPHOS)] (PF ₆ ) [Ru-I- (SEGPHOS)] (ClO ₄ ) [Ru-I- (SEGPHOS) ] (BPh ₄ ) [Ru-I- (SEGPHOS)] (SO ₄ ) [Ru-I- (SEGPHOS)] (CO ₃ )

[Ru-I- (T-SEGPHOS)] (OMs) [Ru-I- (T-SEGPHOS)] (OTs) [Ru-I- (T-SEGPHOS)] (OTf) [Ru-I- (T-SEGPHOS)] ｛OS (O) ₂
C ₄ F ₉ ｝ [Ru-I- (T-SEGPHOS)] (BF ₄ ) [Ru-I- (T-SEGPHOS)] (PF ₆ ) [Ru-I- (T-SEGPHOS)] (ClO ₄ ) [Ru-I- (T-SEGPHOS)] (BPh ₄ ) [Ru-I- (T-SEGPHOS)] (SO ₄ ) [Ru-I- (T-SEGPHOS)] (CO ₃ )

[Ru-I- (tBu-SEGPHOS)] (OMs) [Ru-I- (tBu-SEGPHOS)] (OTs) [Ru-I- (tBu-SEGPHOS)] (OTf) [Ru-I- (TBu-SEGPHOS)] @ OS
(O) ₂ C ₄ F ₀ ｝ [Ru-I- (tBu-SEGPHOS)] (BF ₄ ) [Ru-I- (tBu-SEGPHOS)] (PF ₆ ) [Ru-I- (tBu-SEGPHOS)] (Cl
O ₄ ) [Ru-I- (tBu-SEGPHOS)] (BP
h ₄ ) [Ru-I- (tBu-SEGPHOS)] (SO ₄ ) [Ru-I- (tBu-SEGPHOS)] (CO ₃ )

[Ru-I- (m-T-SEGPHOS)] (OMs) [Ru-I- (m-T-SEGPHOS)] (OTs) [Ru-I- (m-T-SEGPHOS)] (OTf ) [Ru-I- (mT-SEGPHOS)] ｛OS
(O) ₂ C ₄ F ₉ ｝ [Ru-I- (m-T-SEGPHOS)] (BF ₄ ) [Ru-I- (m-T-SEGPHOS)] (PF ₆ ) [Ru-I- (m -T-SEGPHOS)] (Cl
O ₄ ) [Ru-I- (mT-SEGPHOS)] (BP
_{h 4) [Ru-I- (} m-T-SEGPHOS)] (SO 4) [Ru-I- (m-T-SEGPHOS)] (CO 3)

[Ru-I- (DM-SEGPHOS)]
(OMs) [Ru-I- (DM-SEGPHOS)] (OTs) [Ru-I- (DM-SEGPHOS)] (OTf) [Ru-I- (DM-SEGPHOS)] ｛OS (O)
₂ C ₄ F ₉ ｝ [Ru-I- (DM-SEGPHOS)] (BF ₄ ) [Ru-I- (DM-SEGPHOS)] (PF ₆ ) [Ru-I- (DM-SEGPHOS)] (ClO ₄ ) [Ru-I- (DM-SEGPHOS)] (BPh ₄ ) [Ru-I- (DM-SEGPHOS)] (SO ₄ ) [Ru-I- (DM-SEGPHOS)] (CO ₃ ) [Ru-I − (DtBu-SEGPHOS)] (OM
s) [Ru-I- (DtBu-SEGPHOS)] (OT
s) [Ru-I- (DtBu-SEGPHOS)] (OT
f) [Ru-I- (DtBu-SEGPHOS)] ｛OS
(O) ₂ C ₄ F ₉ ｝ [Ru-I- (DtBu-SEGPHOS)] (B
F ₄ ) [Ru-I- (DtBu-SEGPHOS)] (P
F ₆ ) [Ru-I- (DtBu-SEGPHOS)] (ClO
₄ ) [Ru-I- (DtBu-SEGPHOS)] (BPh
₄ ) [Ru-I- (DtBu-SEGPHOS)] (S
O ₄ ) [Ru-I- (DtBu-SEGPHOS)] (C
O ₃ )

[Ru-I- (MeO-SEGPHOS)] (OMs) [Ru-I- (MeO-SEGPHOS)] (OTs) [Ru-I- (MeO-SEGPHOS)] (OTf) [Ru-I- (MeO-SEGPHOS)] @ OS
(O) ₂ C ₄ F ₉ ｝ [Ru-I- (MeO-SEGPHOS)] (BF ₄ ) [Ru-I- (MeO-SEGPHOS)] (PF ₆ ) [Ru-I- (MeO-SEGPHOS)] (Cl
O ₄ ) [Ru-I- (MeO-SEGPHOS)] (BP
h ₄ ) [Ru-I- (MeO-SEGPHOS)] (SO ₄ ) [Ru-I- (MeO-SEGPHOS)] (CO ₃ )

[Ru-I- (p-Cl-SEGPHO)
S)] (OMs) [Ru-I- (p-Cl-SEGPHOS)] (OT
s) [Ru-I- (p-Cl-SEGPHOS)] (OT
f) [Ru-I- (p-Cl-SEGPHOS)] @ OS
(O) ₂ C ₄ F ₉ ｝ [Ru-I- (p-Cl-SEGPHOS)] (B
F ₄ ) [Ru-I- (p-Cl-SEGPHOS)] (P
F ₆ ) [Ru-I- (p-Cl-SEGPHOS)] (ClO
₄ ) [Ru-I- (p-Cl-SEGPHOS)] (BPh
₄ ) [Ru-I- (p-Cl-SEGPHOS)] (S
O ₄ ) [Ru-I- (p-Cl-SEGPHOS)] (C
O ₃ )

[Ru-I- (Naph-SEGPHO)
S)] (OMs) [Ru-I- (Naph-SEGPHOS)] (OT
s) [Ru-I- (Naph-SEGPHOS)] (OT
f) [Ru-I- (Naph-SEGPHOS)] ｛OS
(O) ₂ C ₄ F ₉ ｝ [Ru-I- (Naph-SEGPHOS)] (B
F ₄ ) [Ru-I- (Naph-SEGPHOS)] (P
F ₆ ) [Ru-I- (Naph-SEGPHOS)] (ClO
₄ ) [Ru-I- (Naph-SEGPHOS)] (BPh
₄ ) [Ru-I- (Naph-SEGPHOS)] (S
O ₄ ) [Ru-I- (Naph-SEGPHOS)] (C
O ₃ )

[Ru-I- (cpSEGPHOS)] (OMs) [Ru-I- (cpSEGPHOS)] (OTs) [Ru-I- (cpSEGPHOS)] (OTf) [Ru-I- (cpSEGPHOS)] @ OS (O) ₂
C ₄ F ₉ ｝ [Ru-I- (cpSEGPHOS)] (BF ₄ ) [Ru-I- (cpSEGPHOS)] (PF ₆ ) [Ru-I- (cpSEGPHOS)] (ClO ₄ ) [Ru-I- ( cpSEGPHOS)] (BPh ₄ ) [Ru-I- (cpSEGPHOS)] (SO ₄ ) [Ru-I- (cpSEGPHOS)] (CO ₃ ) [Ru-I- (CySEGPHOS)] (OMs) [Ru-I- (CySEGPHOS)] (OTs) [Ru-I- (CySEGPHOS)] (OTf) [Ru-I- (CySEGPHOS)] ｛OS (O) _{2
C 4 F 9} [Ru-} I- (CySEGPHOS)] (BF 4) [Ru-I- (CySEGPHOS)] (PF 6) [Ru-I- (CySEGPHOS)] (ClO 4) [Ru-I- ( CySEGPHOS)] (BPh ₄ ) [Ru-I- (CySEGPHOS)] (SO ₄ ) [Ru-I- (CySEGPHOS)] (CO ₃ )

[Ru-I- (SEGPHOS)] ｛OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru-I- (T-SEGPHOS)] ｛OS (O) ₂
C ₈ F ₁₇ ｝ [Ru-I- (tBu-SEGPHOS)] ｛OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru-I- (mT-SEGPHOS)] ｛OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru-I- (DM-SEGPHOS)] ｛OS (O)
₂ C ₈ F ₁₇ ｝ [Ru-I- (DtBu-SEGPHOS)] ｛OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru-I- (MeO-SEGPHOS)] ｛OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru-I- (p-Cl-SEGPHOS)] ｛OS
(O) ₂ C ₈ F ₁₇ ｝ [Ru-I- (cpSEGPHOS)] ｛OS (O) ₂
C ₈ F ₁₇ ｝ [Ru-I- (CySEGPHOS)] ｛OS (O) ₂
C ₈ F ₁₇ ｝

[Ru (I) _1.5 (SEGPHOS)] ₂ (OMs) [Ru (I) _1.5 (SEGPHOS)] ₂ (OTs) [Ru (I) _1.5 (SEGPHOS)] ₂ (OTf) [Ru (I) _1.5 (SEGPHOS)] ₂ @OS (O)
₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (SEGPHOS)] ₂ (BF ₄ ) [Ru (I) _1.5 (SEGPHOS)] ₂ (PF ₆ ) [Ru (I) _1.5 (SEGPHOS)] ₂ (ClO ₄ ) [Ru (I) _1.5 (SEGPHOS)] ₂ (BPh ₄ ) [Ru (I) _1.5 (T-SEGPHOS)] ₂ (OM
s) [Ru (I) _1.5 (T-SEGPHOS)] ₂ (OT
s) [Ru (I) _1.5 (T-SEGPHOS)] ₂ (OT
f) [Ru (I) _1.5 (T-SEGPHOS)] ₂ @ OS
(O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (T-SEGPHOS)] ₂ (B
F ₄ ) [Ru (I) _1.5 (T-SEGPHOS)] ₂ (P
F ₆ ) [Ru (I) _1.5 (T-SEGPHOS)] ₂ (ClO
₄ ) [Ru (I) _1.5 (T-SEGPHOS)] ₂ (BPh
₄ )

[Ru (I) _1.5 (tBu-SEGPHO)
S)] ₂ (OMs) [Ru (I) _1.5 (tBu-SEGPHOS)] ₂ (O
Ts) [Ru (I) _1.5 (tBu-SEGPHOS)] ₂ (O
Tf) [Ru (I) _1.5 (tBu-SEGPHOS)] ₂ ｛O
S (O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (tBu-SEGPHOS)] ₂ (B
F ₄ ) [Ru (I) _1.5 (tBu-SEGPHOS)] ₂ (P
F ₆ ) [Ru (I) _1.5 (tBu-SEGPHOS)] ₂ (C
lO ₄ ) [Ru (I) _1.5 (tBu-SEGPHOS)] ₂ (B
Ph ₄ ) [Ru (I) _1.5 (m-T-SEGPHOS)] ₂ (O
Ms) [Ru (I) _1.5 (mT-SEGPHOS)] ₂ (O
Ts) [Ru (I) _1.5 (m-T-SEGPHOS)] ₂ (O
Tf) [Ru (I) _1.5 (m-T-SEGPHOS)] ₂ ｛O
S (O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (m-T-SEGPHOS)] ₂ (B
F ₄ ) [Ru (I) _1.5 (m-T-SEGPHOS)] ₂ (P
F ₆ ) [Ru (I) _1.5 (m-T-SEGPHOS)] ₂ (C
lO ₄ ) [Ru (I) _1.5 (m-T-SEGPHOS)] ₂ (B
Ph ₄ )

[Ru (I) _1.5 (DM-SEGPHO)
S)] ₂ (OMs) [Ru (I) _1.5 (DM-SEGPHOS)] ₂ (OT
s) [Ru (I) _1.5 (DM-SEGPHOS)] ₂ (OT
f) [Ru (I) _1.5 (DM-SEGPHOS)] ₂ @ OS
(O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (DM-SEGPHOS)] ₂ (BF
₄ ) [Ru (I) _1.5 (DM-SEGPHOS)] ₂ (PF
₆ ) [Ru (I) _1.5 (DM-SEGPHOS)] ₂ (Cl
O ₄ ) [Ru (I) _1.5 (DM-SEGPHOS)] ₂ (BP
_{h 4) [Ru (I)} 1.5 (DtBu-SEGPHOS)]
₂ (OMs) [Ru (I) _1.5 (DtBu-SEGPHOS)]
₂ (OTs) [Ru (I) _1.5 (DtBu-SEGPHOS)]
₂ (OTf) [Ru (I) _1.5 (DtBu-SEGPHOS)]
₂ {OS (O) ₂ C ₄ F ₉ } [Ru (I) _1.5 (DtBu-SEGPHOS)]
₂ (BF ₄ ) [Ru (I) _1.5 (DtBu-SEGPHOS)]
₂ (PF ₆ ) [Ru (I) _1.5 (DtBu-SEGPHOS)]
₂ (ClO ₄ ) [Ru (I) _1.5 (DtBu-SEGPHOS)]
₂ (BPh ₄₎

[Ru (I) _1.5 (MeO-SEGPHO)
S)] ₂ (OMs) [Ru (I) _1.5 (MeO-SEGPHOS)] ₂ (O
Ts) [Ru (I) _1.5 (MeO-SEGPHOS)] ₂ (O
Tf) [Ru (I) _1.5 (MeO-SEGPHOS)] ₂ ｛O
S (O) ₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (MeO-SEGPHOS)] ₂ (B
F ₄ ) [Ru (I) _1.5 (MeO-SEGPHOS)] ₂ (P
F ₆ ) [Ru (I) _1.5 (MeO-SEGPHOS)] ₂ (C
lO ₄ ) [Ru (I) _1.5 (MeO-SEGPHOS)] ₂ (B
Ph ₄ ) [Ru (I) _1.5 (p-Cl-SEGPHOS)]
₂ (OMs) [Ru (I) _1.5 (p-Cl-SEGPHOS)]
₂ (OTs) [Ru (I) _1.5 (p-Cl-SEGPHOS)]
₂ (OTf) [Ru (I) _1.5 (p-Cl-SEGPHOS)]
₂ {OS (O) ₂ C ₄ F ₉ } [Ru (I) _1.5 (p-Cl-SEGPHOS)]
₂ (BF ₄ ) [Ru (I) _1.5 (p-Cl-SEGPHOS)]
₂ (PF ₆ )

[RuI (HCOO) (BIPHEP)] ₂ [RuI (HCOO) (BICHEP)] ₂ [RuI (HCOO) (MBIPHEP)] ₂ [RuI (HCOO) (MBICHEP)] ₂ [RuI (CH ₃ COO) (BIPHEP)] ₂ [RuI (CH ₃ COO) (BICHEP)] ₂ [RuI (CH ₃ COO) (MBIPHEP)] ₂ [RuI (CH ₃ COO) (MBICHEP)] ₂ [RuI (CH ₃ CH ₂ COO) (BIPHEP) ₂ [RuI (CH ₃ CH ₂ COO) (BICHEP)] ₂ [RuI (CH ₃ CH ₂ COO) (MBIPHEP)]
₂ [RuI (CH ₃ CH ₂ COO) (MBICEP)]
₂ [RuI (CH ₃ CH ₂ CH ₂ COO) (BIPHE
P)] ₂ [RuI (CH ₃ CH ₂ CH ₂ COO) (BICHE
P)] ₂ [RuI (CH ₃ CH ₂ CH ₂ COO) (MBIPHE
P)] ₂ [RuI (CH ₃ CH ₂ CH ₂ COO) (MBICHE
P)] ₂

[RuI (CH ₃ COCO) (BIPHEP)] ₂ [RuI (CH ₃ COCO) (BICHEP)] ₂ [RuI (CH ₃ COCO) (MBIPHEP)] ₂ [RuI (CH ₃ COCO) (MBICEP)] ₂ [RuI (PhCOO) (BIPHEP)] ₂ [RuI (PhCOO) (BICHEP)] ₂ [RuI (PhCOO) (MBIPHEP)] ₂ [RuI (PhCOO) (MBICHEP)] ₂ [RuI (CF ₃ COO) (BIPHEP) )] ₂ [RuI (CF ₃ COO) (BICHEP)] ₂ [RuI (CF ₃ COO) (MBIPHEP)] ₂ [RuI (CF ₃ COO) (MBICHEP)] ₂

[Ru-I- (BIPHEP)] ₂ (OMs) [Ru-I- (BIPHEP)] ₂ (OTs) [Ru-I- (BIPHEP)] ₂ (OTf) [Ru-I- (BIPHEP) ] ₂ @OS (O) ₂ C ₄
F ₉ ｝ [Ru-I- (BIPHEP)] ｛OS (O) ₂ C ₈ F
₁₇ ｝ [Ru-I- (BIPHEP)] ₂ (BF ₄ ) [Ru-I- (BIPHEP)] ₂ (PF ₆ ) [Ru-I- (BIPHEP)] ₂ (ClO ₄ ) [Ru-I- ( BIPHEP)] ₄ (BPh ₄ ) [Ru-I- (BIPHEP)] (SO ₄ ) [Ru-I- (BIPHEP)] (CO ₃ )

[Ru (I) _1.5 (BIP HEP)] ₂ (OMs) [Ru (I) _1.5 (BIP HEP)] ₂ (OTs) [Ru (I) _1.5 (BIP HEP)] ₂ (OTf) [Ru (I) _1.5 (BIPHEP)] ₂ ｛OS (O) ₂
C ₄ F ₉ ｝ [Ru (I) _1.5 (BIPHEP)] ₂ (BF ₄ ) [Ru (I) _1.5 (BIPHEP)] ₂ (PF ₆ ) [Ru (I) _1.5 (BIPHEP)] ₂ (ClO ₄ ) [Ru (I) _1.5 (BIPHEP)] ₂ (BPh ₄ ) [Ru (I) _1.5 (BIPHEP)] ₂ ｛OS (O) ₂
C ₈ F ₁₇ ｝

[Ru-I- (BICHEP)] ₂ (OMs) [Ru-I- (BICHEP)] ₂ (OTs) [Ru-I- (BICHEP)] ₂ (OTf) [Ru-I- (BICHEP) ] ₂ @OS (O) ₂ C ₄
F ₉ ｝ [Ru-I- (BICHEP)] ｛OS (O) ₂ C ₈ F
₁₇ ｝ [Ru-I- (BICHEP)] ₂ (BF ₄ ) [Ru-I- (BICHEP)] ₂ (PF ₆ ) [Ru-I- (BICHEP)] ₂ (ClO ₄ ) [Ru-I- ( [BICHEP)] ₂ (BPh ₄ ) [Ru-I- (BICHEP)] (SO ₄ ) [Ru-I- (BICHEP)] (CO ₃ )

[Ru (I) _1.5 (BICHEP)] ₂ (OMs) [Ru (I) _1.5 (BICHEP)] ₂ (OTs) [Ru (I) _1.5 (BICHEP)] ₂ (OTf) [Ru (I) _1.5 (BICHEP)] ₂ ｛OS (O) ₂
C ₄ F ₉ ｝ [Ru (I) _1.5 (BICHEP)] ₂ (BF ₄ ) [Ru (I) _1.5 (BICHEP)] ₂ (PF ₆ ) [Ru (I) _1.5 (BICHEP)] ₂ (ClO ₄ ) [Ru (I) _1.5 (BICHEP)] ₂ (BPh ₄ ) [Ru (I) _1.5 (BICHEP)] ₂ ｛OS (O) ₂
C ₈ F ₁₇ ｝

[Ru-I- (MBIPHEP)] ₂ (OMs) [Ru-I- (MBIPHEP)] ₂ (OTs) [Ru-I- (MBIPHEP)] ₂ (OTf) [Ru-I- (MBIPHEP) ] ₂ @OS (O) ₂ C
_{4 F 9} [Ru-I-} (MBIPHEP)] {OS (O) 2 C 8
F ₁₇ ｝ [Ru-I- (MBIPHEP)] ₂ (BF ₄ ) [Ru-I- (MBIPHEP)] ₂ (PF ₆ ) [Ru-I- (MBIPHEP)] ₂ (ClO ₄ ) [Ru-I- (MBIPHEP)] ₂ (BPh ₄ ) [Ru-I- (MBIPHEP)] (SO ₄ ) [Ru-I- (MBIPHEP)] (CO ₃ )

[Ru (I) _1.5 (MBIPHEP)] ₂ (OMs) [Ru (I) _1.5 (MBIPHEP)] ₂ (OTs) [Ru (I) _1.5 (MBIPHEP)] ₂ (OTf) [Ru (I) _1.5 (MBIPHEP)] ₂ @OS (O)
₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (MBIPHEP)] ₂ (BF ₄ ) [Ru (I) _1.5 (MBIPHEP)] ₂ (PF ₆ ) [Ru (I) _1.5 (MBIPHEP)] ₂ (ClO ₄ ) [Ru (I) _1.5 (MBIPHEP)] ₂ (BPh ₄ ) [Ru (I) _1.5 (MBIPHEP)] ₂ ｛OS (O)
₂ C ₈ F ₁₇ ｝

[Ru-I- (MBICHEP)] ₂ (OMs) [Ru-I- (MBICHEP)] ₂ (OTs) [Ru-I- (MBICHEP)] ₂ (OTf) [Ru-I- (MBICHEP) ] ₂ @OS (O) ₂ C
₄ F ₉ ｝ [Ru-I- (MBICEP)] ｛OS (O) ₂ C ₈
F ₁₇ ｝ [Ru-I- (MBICHEP)] ₂ (BF ₄ ) [Ru-I- (MBICHEP)] ₂ (PF ₆ ) [Ru-I- (MBICHEP)] ₂ (ClO ₄ ) [Ru-I- (MBICHEP)] ₂ (BPh ₄ ) [Ru-I- (MBICHEP)] (SO ₄ ) [Ru-I- (MBICHEP)] (CO ₃ )

[Ru (I) _1.5 (MBICHEP)] ₂ (OMs) [Ru (I) _1.5 (MBICHEP)] ₂ (OTs) [Ru (I) _1.5 (MBICHEP)] ₂ (OTf) [Ru (I) _1.5 (MBICEP)] ₂ @OS (O)
₂ C ₄ F ₉ ｝ [Ru (I) _1.5 (MBICHEP)] ₂ (BF ₄ ) [Ru (I) _1.5 (MBICHEP)] ₂ (PF ₆ ) [Ru (I) _1.5 (MBICHEP)] ₂ (ClO ₄ ) [Ru (I) _1.5 (MBICHEP)] ₂ (BPh ₄ ) [Ru (I) _1.5 (MBICHEP)] ₂ ｛OS (O) ₂
C ₈ F ₁₇ ｝

The thus obtained formula (1) of the present invention [Ru
-(I) _q- (T ¹ ) _n (L)] _m (T ² ) _p has extremely high catalytic activity and is a compound that can be widely used as a catalyst for asymmetric synthesis. In particular, if this compound is used as a catalyst for the asymmetric hydrogenation of 4-methylene-2-oxetanone, the optical activity of high optical purity can be improved in a short time.
-Methyl-2-oxetanone can be produced.

[Ru- (I) _q- (T ¹ )]
_n (L)] _m (T ² ) _p Optical activity 4-
To produce methyl-2-oxetanone, for example, in a pressure vessel under a nitrogen atmosphere, as described in the above specific example, [RuI (RCOO) (R ¹ -BINAP)] ₂ ,
4-Methylene-2-oxetanone as a raw material compound and a solvent are added, and the mixture is reacted at a hydrogen pressure of 5 to 150 kg / cm ² . 4-methylene-2-used as a starting compound
Oxetanone is described, for example, in R.S. J. The method reported by Clemens et al. (RJ Clemens et al., Chem. Rev., Vol. 8
6, pp. 241-318 (1986)), and can be easily obtained by synthesis by thermally decomposing acetic acid or acetic anhydride.

The asymmetric hydrogenation catalyst [RuI (RCO
O) (R ¹ -BINAP)] ₂ can obtain 4-methyl-2-oxetanone having a desired absolute configuration by selecting either the (R) form or the (S) form.

In order to advantageously carry out the production of optically active 4-methyl-2-oxetanone, [RuI (RCO
O) (R ¹ -BINAP)] ₂ has a molar ratio of metal ruthenium to optically active phosphine of 1: 1.05 to 1: 0.
It is preferable to use one prepared at a ratio of 95. Usually, when preparing the optically active complex represented by the formula (3), about 1.0 equivalent of the optically active phosphine ligand is added to 1 equivalent of ruthenium.
Although 5 to 1.2 equivalents are used, the use of one having an amount less than 1.05 equivalents can prevent a polymerization reaction of 4-methylene-2-oxetanone which is a side reaction. If the amount of the optically active phosphine ligand is less than 0.95 equivalent, the amount of metal ruthenium becomes excessive, which is uneconomical.

The catalyst [RuI (RCOO) (R ^1-
BINAP)] ₂ is used in an amount of usually about 0.0 with respect to 1 mol of 4-methylene-2-oxetanone as the starting compound.
It is preferably in the range of 001 to 0.01 mol, particularly preferably in the range of about 0.0002 to 0.0005 mol.
When the amount of the catalyst is less than 0.0001 mol, the effect as a catalyst is not sufficiently exhibited, and when the amount is more than 0.0005 mol, it becomes uneconomical.

The solvent is not particularly limited as long as it is a solvent used for ordinary asymmetric hydrogenation, and specific examples thereof include linear or cyclic ethers such as diethyl ether, tetrahydrofuran and dioxane; Organic halides such as methylene chloride, methylene bromide and dichloroethane; ketones such as acetone, methyl ethyl ketone and methyl butyl ketone; carboxylic acids such as acetic acid and propionic acid; esters such as ethyl acetate, butyl acetate and methyl 3-hydroxybutyrate. , Toluene, benzene and other aromatic compounds, methano-
And alcohols such as ethanol, ethanol, isopropanol, tert-butyl alcohol and 1,3-butanediol, and mixed solvents thereof. further,
To increase the speed of the asymmetric hydrogenation reaction, about 1% of water may be added to the above solvent.

The reaction temperature and reaction time for the asymmetric hydrogenation vary depending on the type of the catalyst and other reaction conditions, but are usually from room temperature to 100 ° C., particularly preferably from about 30 to 60 ° C., and from about 0.5 to about 0.5 to about 60 to about 60 ° C. It is good to react for 40 hours. The hydrogen pressure is about 5 to 150 kg / cm ² , preferably about 20 to 100 kg / cm ² .
The desired optically active 4-methyl-2-oxetanone can be obtained by purifying the reaction product by a method such as distillation. Other catalysts can be reacted under similar conditions.

[0092]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following examples, the following instruments were used for measuring the physical properties of the obtained compounds. ³¹ P-NMR spectrum: AM-400 type device (manufactured by Bruker) External standard substance; 85% phosphoric acid solvent; chloroform (optical purity measurement) Gas chromatograph: HEWLETT PACKARD 5890 SERIE
S II optically active column (Chraldex G-TA 30m (ASTEC))

Example 1 [RuI (CH ₃ COO) ((S) -T-BINA]
P)] Production of ₂ : After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmol) of [RuI ₂ (p-cymene)] ₂ was added.
1.41 g (2.07 mmol) of (S) -T-BINAP and 40 ml of methanol were added, and the mixture was stirred at 55 ° C for 16 hours. Then, after cooling to room temperature and collecting methanol, 0.172 g (2.09 mmol) of sodium acetate was added under nitrogen, 20 ml of methylene chloride and 20 ml of degassed water were added, and the mixture was stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 1.9 g (96.4% yield) of the title compound were obtained. ³¹ P-NMR spectrum: 20.5 (d, J = 45 Hz), 74.6 (d,
46Hz)

Example 2 [RuI (CH ₃ COO) ((S) -T-BINA]
P)] Production of ₂ : After replacing a 200 ml reaction vessel with nitrogen,
[RuI (p-cymene) ((S) -T-BINAP)] I
2.7 g (2.31 mmol) and 110 ml of methanol were added, and the mixture was stirred at 55 ° C. for 16 hours. After cooling to room temperature and collecting methanol, 0.199 g of sodium acetate was added under nitrogen.
(2.42 mmol), 20 ml of methylene chloride and 20 ml of degassed water were added, and the mixture was stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 2.2 g (98.6% yield) of the title compound were obtained.

Example 3 [RuI (CH ₃ COO) ((S) -T-BINA]
P)] Production of ₂ : After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmol) of [RuI ₂ (p-cymene)] ₂ was added.
1.41 g (2.07 mmol) of (S) -T-BINAP, 0.172 g (2.09 mmol) of sodium acetate and 40 ml of methanol were added, and the mixture was stirred at 55 ° C. for 16 hours. Thereafter, the mixture was cooled to room temperature, and methanol was recovered under reduced pressure. Then, 20 ml of methylene chloride and 20 ml of degassed water were added under nitrogen, and the mixture was stirred for 10 minutes. The methylene chloride layer was removed with a syringe, washed with degassed water (20 ml), and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at room temperature for 4 hours. 1.9 g (96.4% yield) of the title compound were obtained.

Example 4 [RuI (CH ₃ COO) ((S) -T-BINA]
P)] Production of ₂ : After replacing a 200 ml reaction vessel with nitrogen,
[RuI (p-cymene) ((S) -T-BINAP)] I
2.7 g (2.31 mmol) and 0.199 g (2.42 mmo
l), 110 ml of methanol was added, and the mixture was stirred at 55 ° C for 16 hours. Then, after cooling to room temperature and collecting methanol, 20 ml of methylene chloride and 20 ml of degassed water were added under nitrogen, and the mixture was stirred for 30 minutes. The methylene chloride layer is removed with a syringe, washed with 20 ml of degassed water, and methylene chloride is distilled off under reduced pressure.
It was dried under reduced pressure at 30 ° C. for 4 hours. 2.2 g of the title compound (yield
98.6%).

Example 5 [RuI (CH ₃ CH ₂ COO) ((S) -T-BIN]
AP)] ₂ : After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmo) of [RuI ₂ (p-cymene)] ₂ was added.
l), 1.41 g (2.07 mmol) of (S) -T-BINAP and 40 ml of methanol were added, and the mixture was stirred at 55 ° C for 16 hours. afterwards,
After cooling to room temperature and collecting methanol, 0.2 g (2.08 mmol) of sodium propionate was added under nitrogen, and methylene chloride 20
ml and 20 ml of degassed water were added and stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 1.9 g (95.0% yield) of the title compound was obtained. ³¹ P-NMR spectrum: 20.5 (d, J = 43 Hz), 73.9 (d,
J = 43Hz)

Example 6 [RuI (PhCOO) ((S) -T-BINAP)]
Production of ₂ : After replacing the 80 ml Schlenk tube with nitrogen,
[RuI ₂ (p-cymene)] ₂ (1.0 g, 1.02 mmol),
1.41 g (2.07 mmol) of (S) -T-BINAP and 40 ml of methanol were added, and the mixture was stirred at 55 ° C for 16 hours. After cooling to room temperature and recovering methanol, 0.301 g (2.09 mmol) of sodium benzoate was added under nitrogen, and 20 ml of methylene chloride was added.
20 ml of degassed water was added and stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 2.0 g (95.4% yield) of the title compound was obtained. ³¹ P-NMR spectrum: 21.1 (d, J = 44 Hz), 74.2
(D, J = 44Hz)

Example 7 [RuI (CF ₃ COO) ((S) -T-BINA]
P)] Production of ₂ : After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmol) of [RuI ₂ (p-cymene)] ₂ was added.
1.41 g (2.07 mmol) of (S) -T-BINAP and 40 ml of methanol were added, and the mixture was stirred at 55 ° C for 16 hours. After cooling to room temperature and collecting methanol, methylene chloride was charged with 1.11 g (8.16 mmol) of sodium trifluoroacetate under nitrogen.
20 ml and 20 ml of degassed water were added and stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 1.9 g (91.3% yield) of the title compound was obtained.

Example 8 [RuI (CH ₃ COOO) ((S) -T-BINA]
P)] Production of ₂ : After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmol) of [RuI ₂ (p-cymene)] ₂ was added.
1.41 g (2.07 mmol) of (S) -T-BINAP and 40 ml of methanol were added, and the mixture was stirred at 55 ° C for 16 hours. Then, after cooling to room temperature and collecting methanol, 0.228 g (2.07 mmol) of sodium pyruvate was added under nitrogen, and methylene chloride 20 m
l, 20 ml of degassed water was added and stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 1.9 g (93.7% yield) of the title compound was obtained. ³¹ P-NMR spectrum: 21.5 (d, J = 44 Hz), 72.8
(D, J = 44Hz)

Example 9 [RuI (CH ₃ COO) ((S) -BINAP)] ₂
Production: After replacing the 80 ml Schlenk tube with nitrogen, [R
uI ₂ (p-cymene)] ₂ (1.0 g, 1.02 mmol), (S)-
1.28 g (2.06 mmol) of BINAP, 40 ml of methanol
And stirred at 55 ° C. for 16 hours. After cooling to room temperature and collecting methanol, 0.172 g of sodium acetate was added under nitrogen.
(2.09 mmol), 20 ml of methylene chloride and 20 ml of degassed water were added, and the mixture was stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 1.8 g (97.0% yield) of the title compound was obtained.

Example 10 [RuI (CH ₃ COO) ((S) -tBu-BINA]
P)] Production of ₂ : After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmol) of [RuI ₂ (p-cymene)] ₂ was added.
1.75 g (2.06 mmol) of (S) -tBu-BINAP and 40 ml of methanol were added, and the mixture was stirred at 55 ° C for 16 hours. Then, after cooling to room temperature and collecting methanol, 0.172 g (2.09 mmol) of sodium acetate was added under nitrogen, and methylene chloride 20 m
l, 20 ml of degassed water was added and stirred for 16 hours. The methylene chloride layer was taken with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 40 ° C. for 4 hours. This gave 2.2 g (yield 95.1%) of the title compound.

Example 11 RuI (CH ₃ COO) ((S) -DM-BINA
Production of P)] ₂ : After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmo) of [RuI ₂ (p-cymene)] ₂ was added.
l), 1.52 g (2.07 mmol) of (S) -DM-BINAP,
40 ml of methanol was added, and the mixture was stirred at 55 ° C for 16 hours. Then, after cooling to room temperature and collecting methanol, 0.172 g (2.09 mmol) of sodium acetate was added under nitrogen, and methylene chloride 20 m
l, 20 ml of degassed water was added and stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 2.0 g (95.9% yield) of the title compound was obtained.

Example 12 Production of (R) -4-methyl-2-oxetanone: 500 ml
In a stainless steel autoclave of capacity, under nitrogen atmosphere,
[RuI (CH ₃ COO) ((S) -BINAP)] ₂
76.65 mg (0.0794 mmol), 20.1 g (239.3 mmol) of 4-methylene-2-oxetanone, 80 m of tetrahydrofuran
and 0.45 ml of degassed water, and stirred at a hydrogen pressure of 50 kg / cm ² and a reaction temperature of 50 ° C. for 15 hours. The obtained reaction solution was distilled using a Claisen tube distillation apparatus to obtain 18.0 g (yield: 87.5%) of a fraction having a boiling point of 71 to 73 ° C / 29 mmHg. The conversion of this reaction is 87.
The catalyst activity was 5630 and the turnover number was 2630. The product was confirmed to be 4-methyl-2-oxetanone as a result of comparative analysis with a sample by gas chromatography, and was found to be an optically active column (Chiraldex G-TA30) manufactured by ASTEC.
Gas chromatography (GC) measurement using m) confirmed that the absolute configuration was (R) and the optical purity was 94.3% ee.

Example 13 Production of (R) -4-methyl-2-oxetanone: [Ru
I (PhCOO) ((S) -T-BINAP)] ₂ 81.
58 mg (0.0794 mmol), 4-methylene-2-oxetanone 20.
The reaction was carried out in the same manner as in Example 12 except that 69 g (246.31 mmol) was used to obtain 17.0 g (yield: 80.3%) of the title compound. The conversion of this reaction was 80.1%, and the catalytic activity was 2,480 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 95.3% ee.

Example 14 Production of (R) -4-methyl-2-oxetanone: [Ru
I (CH ₃ CH ₂ COO) ((S) -T-BINA
_{P)] 2 77.76 mg (0.0794} mmol), 4- methylene-2-oxetanone 20.37 g (242.5 mmol) except using the A reaction was conducted in the same manner as in Example 12, the title compound 15.6 g (yield:
74.8%). The conversion of this reaction was 74.97% and the catalytic activity was 2290 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 94.9% ee.

Example 15 Preparation of (R) -4-methyl-2-oxetanone: [Ru
_{I (CH 3 COCOO) ((} S) -T-BINAP)]
_{2 47.32 mg (0.0 476 mmol)} , 4-methylene-2-oxetanone 20.42 g (243.1 mmol) but using Example 1
Reaction was carried out in the same manner as in Example 2 to obtain 10.6 g of the title compound (yield 50.7 g).
%). The conversion of this reaction was 50.73% and the catalytic activity was 2590 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 94.3% ee.

Example 16 Preparation of (R) -4-methyl-2-oxetanone: [Ru
_{I (CF 3 COO) ((} S) -T-BINAP)] 2 6
8.42 mg (0.068 mmol), 4-methylene-2-oxetanone 2
The reaction was carried out in the same manner as in Example 12 except that 0.0 g (238.1 mmol) was used to obtain 15.3 g (yield: 74.7%) of the title compound. The conversion of this reaction was 75.0%, and the catalytic activity was 2630 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 94.0% ee.

Example 17 Production of (R) -4-methyl-2-oxetanone: [Ru
_{I (CH 3 COO) ((} S) -BINAP)] 2 61.81
mg (0.068 mmol), 4-methylene-2-oxetanone 20.2
The reaction was carried out in the same manner as in Example 12 except that 7 g (241.3 mmol) was used to obtain 14.5 g (yield 69.9%) of the title compound. The conversion of this reaction was 69.9%, and the catalyst activity was 2,480 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 94.0% ee.

Example 18 Production of (R) -4-methyl-2-oxetanone: [Ru
I (CH ₃ COO) ((S) -tBu-BINAP)]
_{2 77.12 mg (0.068 mmol),} 4- methylene-2-oxetanone 20.5 g (244.0 mmol) except using the A reaction was conducted in the same manner as in Example 12 to give the title compound 14.6 g (69.5% yield) . The conversion of this reaction was 69.7%, and the catalytic activity was 2500 turnover. The absolute configuration of the product was (R) -form and the optical purity was 94.1% ee.

Example 19 Production of (R) -4-methyl-2-oxetanone: [Ru
_{I (CH 3 COO) ((} S) -DM-BINAP)] 2
69.5 mg (0.068 mmol), 4-methylene-2-oxetanone 2
The reaction was carried out in the same manner as in Example 12 except that 0.0 g (238.1 mmol) was used, thereby obtaining 15.2 g (yield: 74.2%) of the title compound. The conversion of this reaction was 74.2%, and the catalytic activity was 2600 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 94.2% ee.

Example 20 [Ru-I _1.5 -{(S) -T-BINAP}] ₂ (O
Production of Tf): After replacing the 80 ml Schlenk tube with nitrogen,
0.5 g (0.51 mmol) of [RuI ₂ (p-cymene)] ₂
0.7 g (1.03 mmol) of (S) -T-BINAP and 20 ml of methanol were added, and the mixture was stirred at 55 ° C. for 16 hours. Thereafter, the mixture was cooled to room temperature, and methanol was recovered.
(0.51 mmol), methylene chloride (20 ml) and degassed water (20 ml) were added, and the mixture was stirred for 16 hours. Take the methylene chloride layer with a syringe,
After washing with 20 ml of degassed water and distilling off methylene chloride under reduced pressure, the obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. Title compound
1.05 g (97.5% yield) was obtained. ³¹ P-NM of product compound
The R spectrum is shown below. ³¹ P-NMR spectrum: 1.8 (d, J = 35 Hz), 4.6 (d, J
= 33Hz), 75.0 (d, J = 34Hz), 76.4 (d, J = 36Hz)

FIG. 1 is an overall view of the LC mass spectrum of the produced compound, and FIG. 2 is an enlarged view of a portion having a molecular weight of 1950 to 2030. (The measurement condition of the LC mass spectrum is H
PLC conditions: apparatus; HP1100, mobile phase; dichloromethane, sample diluting solvent; dichloromethane, MS conditions:
Equipment: Micromass QUATTRO LC, ionization mode; ESI +. In FIG. 2, the peak at 1972.9 is considered to be due to the structure shown below, that is, methanol added only to the cation portion of the product compound.

[Ru-I _1.5 -｛(S) -T-BINA]
P｝] ₂ ⁺⁺ (CH ₃ OH)

[Example 21] [Ru-I _1.5 -{(S) -T-BINAP}] ₂ (O
Production of Tf): After replacing a 200 ml reaction vessel with nitrogen,
[RuI (p-cymene) {(S) T-BINAP}] I
2.7 g (2.31 mmol) and methanol (110 ml) at 55 ° C
Stirred for 16 hours. Then, after cooling to room temperature and collecting methanol, 0.416 g (2.42 mmol) of NaOTf was added under nitrogen, and the mixture was stirred for 16 hours. Take the methylene chloride layer with a syringe,
After washing with 20 ml of degassed water and distilling off methylene chloride under reduced pressure, the obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. Title compound
2.2 g (90.2 yield) was obtained.

Example 22 [Ru-I _1.5 -{(S) -T-BINAP}] ₂ (O
Production of Tf): After replacing the 80 ml Schlenk tube with nitrogen,
[RuI ₂ (p-cymene)] ₂ was 1.0 g (1.02 mmol),
1.41 g (2.07 mmol) of (S) -T-BINAP, NaOT
0.36 g (2.09 mmol) of f and 40 ml of methanol
For 16 hours. After cooling to room temperature and collecting methanol under reduced pressure, 20 ml of methylene chloride and 20 ml of degassed water under nitrogen
Was added and stirred for 10 minutes. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 1.9 g (88.2% yield) of the title compound were obtained.

Example 23 [Ru-I _1.5 -{(S) -T-BINAP}] ₂ (O
Production of Tf): After replacing a 200 ml reaction vessel with nitrogen,
[RuI (p-cymene) {(S) T-BINAP}] I
2.7 g (2.31 mmol) and 0.416 g (2.42 mmo) NaOTf
l), 110 ml of methanol was added, and the mixture was stirred at 55 ° C for 16 hours. Then, after cooling to room temperature and collecting methanol, 20 ml of methylene chloride and 20 ml of degassed water were added under nitrogen, followed by stirring for 30 minutes. The methylene chloride layer was taken with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure.
2.2 g of the title compound (yield 90.
2%).

Example 24 [Ru-I _1.5 -{(S) -T-BINAP}] ₂ (O
Production of Ts): After replacing the 80 ml Schlenk tube with nitrogen,
[RuI ₂ (p-cymene)] ₂ was 1.0 g (1.02 mmol),
1.41 g (2.07 mmol) of (S) -T-BINAP and 40 ml of methanol were added, and the mixture was stirred at 55 ° C. for 16 hours. Thereafter, the mixture was cooled to room temperature, and methanol was recovered.
4 g (2.08 mmol) was added, methylene chloride (20 ml) and degassed water (20 ml) were added, and the mixture was stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 2.03 g (yield 92.3%) of the title compound was obtained. ³¹ P-NMR spectrum: 1.8 (d, J = 36 Hz), 4.6 (d, J
= 34Hz), 75.0 (d, J = 34Hz), 76.4 (d, J = 36Hz)

Example 25 [Ru-I _1.5 -{(S) -T-BINAP}] ₂ (O
Production of Ms): After replacing the 80 ml Schlenk tube with nitrogen,
[RuI ₂ (p-cymene)] ₂ was added in an amount of 1.0 g (1.02 mmol),
1.41 g (2.07 mmol) of (S) -T-BINAP and 40 ml of methanol were added, and the mixture was stirred at 55 ° C. for 16 hours. Then, after cooling to room temperature and collecting methanol, NaOMs was reduced to 0.
247 g (2.09 mmol) in methylene chloride 20ml, degassed water 20ml
Was added and stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 2.03 g (yield 99.3%) of the title compound was obtained. ³¹ P-NMR spectrum: 1.8 (d, J = 36 Hz), 4.6 (d, J
= 35Hz), 75.0 (d, J = 35Hz), 76.4 (d, J = 36Hz)

Example 26 [Ru-I _1.5 -{(S) -T-BINAP}] ₂ (P
Production of F ₆ ): After replacing the 80 ml Schlenk tube with nitrogen,
1.0 g (1.02 mmol) of [Ru ₂ (p-cymene)] ₂ , (S)
1.41 g (2.07 mmol) of T-BINAP and 40
ml and stirred at 55 ° C. for 16 hours. Then, after recovering the methanol was cooled to room temperature, the NH ₄ PF ₆ under nitrogen 0.166
g (1.02 mmol), methylene chloride (20 ml) and degassed water (20 ml) were added, and the mixture was stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 2.1 g (yield 97.8%) of the title compound was obtained. ³¹ P-NMR spectrum: 1.8 (d, J = 36 Hz), 4.6 (d, J
= 34Hz), 75.0 (d, J = 34Hz), 76.4 (d, J = 36Hz)

Example 27 [Ru-I _1.5 -{(S) -T-BINAP}] ₂ (C
Production of lO ₄ ): After replacing the 80 ml Schlenk tube with nitrogen, 1.0 g (1.02 mmol) of [RuI ₂ (p-cymene)] ₂ was added.
1.4 g (2.06 mmol) of (S) -T-BINAP and 40 ml of methanol were added, and the mixture was stirred at 55 ° C. for 16 hours. After cooling to room temperature and collecting methanol, add 0.256 g (2.09 mmol) of sodium perchlorate under nitrogen, 20 ml of methylene chloride, degassed water
20 ml was added and stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 1.95 g (yield 95.0%) of the title compound was obtained. ³¹ P-NMR spectrum: -15.1 (sep, J = 712 Hz), 1.8
(d, J = 35 Hz), 4.6 (d, J = 34 Hz), 75.0 (d, J = 34 Hz), 7
6.4 (d, J = 35Hz)

Example 28 [Ru-I _1.5 -{(S) -BINAP}] ₂ (OT
Production of f): After replacing the 80 ml Schlenk tube with nitrogen,
[RuI ₂ (p-cymene)] ₂ was added in an amount of 1.0 g (1.02 mmol),
1.28 g (2.06 mmol) of (S) -BINAP and methanol
40 ml was added and stirred at 55 ° C. for 16 hours. After cooling to room temperature and collecting methanol, 0.36 g of NaOTf was added under nitrogen.
(2.09 mmol), methylene chloride (20 ml) and degassed water (20 ml) were added, the mixture was stirred for 16 hours, washed with degassed water (20 ml), methylene chloride was distilled off under reduced pressure, and the obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. . 1.95 g (95.7% yield) of the title compound were obtained.

Example 29 [Ru-I _1.5 -{(S) -tBu-BINAP}] ₂
Production of (OTf): After replacing an 80 ml Schlenk tube with nitrogen, 1.0 g (1.02 mmol) of [RuI ₂ (p-cymene)] ₂ was added.
1.75 g (2.06 mmol) of (S) -ptBu-BINAP,
40 ml of methanol was added, and the mixture was stirred at 55 ° C. for 16 hours. Then, after cooling to room temperature and collecting methanol, Na was added under nitrogen.
0.36 g (2.09 mmol) of OTf was added, 20 ml of methylene chloride and 20 ml of degassed water were added, and the mixture was stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 2.4 g (yield 96.1%) of the title compound was obtained.

Example 30 Ru-I _1.5 -{(S) -DM-BINAP}
Production of ₂ (OTf): After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmo) of [RuI ₂ (p-cymene)] ₂ was added.
l), 1.52 g (2.07 mmol) of (S) -DM-BINAP and 40 ml of methanol were added, and the mixture was stirred at 55 ° C for 16 hours. afterwards,
After cooling to room temperature and collecting methanol, NaOT under nitrogen
0.344 g (2.0 mmol) of f in methylene chloride 20 ml, degassed water
20 ml was added and stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 2.2 g (96.99% yield) of the title compound were obtained.

Example 31 Production of (R) -4-methyl-2-oxetanone: 500 ml
In a stainless steel autoclave of capacity, under nitrogen atmosphere,
[Ru-I _1.5 -{(S) -T-BINAP}] ₂ (O
Tf) 45.71 g (0.0433 mmol), 20.32 g (241.905 mmol) of 4-methylene-2-oxetanone, 80 ml of tetrahydrofuran and 0.45 ml of degassed water were charged, and the mixture was stirred at a hydrogen pressure of 50 kg / cm ² and a reaction temperature of 50 ° C. for 15 hours. . The obtained reaction solution was distilled using a Claisen tube distillation apparatus, and the boiling point was 71 to 73 ° C / 29 mmHg.
A fraction 16.9 (81.2% yield) was obtained. The conversion of this reaction is
The catalyst activity was 81.42% and the turnover number was 4550.
The product was confirmed to be 4-methyl-2-oxetanone as a result of comparative analysis with a sample by gas chromatography.
Gas chromatography (GC) measurement using A30m) confirmed that the absolute configuration was (R) and the optical purity was 94.5% ee.

Example 32 Production of (R) -4-methyl-2-oxetanone: [Ru
−I _1.5 − {(S) -T-BINAP}] ₂ (OTs)
Example 31 except that 85.55 mg (0.0794 mmol) and 20.25 g (241.07 mmol) of 4-methylene-2-oxetanone were used.
The reaction was carried out in the same manner as described above, and the title compound (20.45 g, yield 98.64) was obtained.
%). The conversion of this reaction was 98.64% and the catalytic activity was 2,990 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 95.6% ee.

Example 33 Production of (R) -4-methyl-2-oxetanone: [Ru
−I _1.5 − {(S) -T-BINAP}] ₂ (OMs)
Example 31 except that 47.71 mg (0.0476 mmol) and 20.42 g (243.1 mmol) of 4-methylene-2-oxetanone were used.
The reaction was carried out in the same manner as described above to obtain 11.1 g of the title compound (yield 53.1 g).
%). The conversion of this reaction was 53.1%, and the catalytic activity was 2710 in turnover number. The absolute configuration of the product was (R) -form and the optical purity was 94.1% ee.

Example 34 Production of (R) -4-methyl-2-oxetanone [Ru
−I _1.5 − {(S) -T-BINAP}] ₂ (PF ₆ )
Example 31 except that 50.94 mg (0.0484 mmol) and 20.46 g (243.57 mmol) of 4-methylene-2-oxetanone were used.
The reaction was carried out in the same manner as described above to obtain 16.3 g of the title compound (yield: 77.8 g).
%). The conversion of this reaction was 77.80% and the catalytic activity was 3910 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 94.7% ee.

Example 35 Production of (R) -4-methyl-2-oxetanone: [Ru
-I _1.5 -{(S) -T-BINAP}] ₂ (Cl
The reaction was carried out in the same manner as in Example 31 except that 47.91 mg (0.0476 mmol) of O ₄ ) and 20.29 g (241.55 mmol) of 4-methylene-2-oxetanone were used, and 15.9 g of the title compound (yield)
76.5%). The conversion of this reaction was 76.5%, and the catalytic activity was 3880 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 95.8% ee.

Example 36 Production of (R) -4-methyl-2-oxetanone [Ru
−I _1.5 − {(S) -BINAP}] ₂ (OTf) 47.9
1 mg (0.0479 mmol), 4-methylene-2-oxetanone
The reaction was carried out in the same manner as in Example 31 except that 20.0 g (238.1 mmol) was used to obtain 15.9 g (yield 77.65%) of the title compound. The conversion of this reaction was 77.65% and the catalytic activity was 3860 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 95.0% ee.

Example 37 Production of (R) -4-methyl-2-oxetanone: [Ru
-I _1.5 -{(S) -ptBu-BINAP}]
_The reaction was carried out in the same manner as in Example 31 except that 70.73 mg (0.0476 mmol) of ₂ (OTf) and 20.34 g (242.14 mmol) of 4-methylene-2-oxetanone were used, and the title compound 12.4 was obtained.
g (yield 59.55%) was obtained. The conversion of this reaction is 59.65
%, Catalytic activity was 3030 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 95.8% ee.

Example 38 Production of (R) -4-methyl-2-oxetanone [Ru
-I _1.5 -{(S) -DM-BINAP}] ₂ (OT
f) Example 31 except that 69.5 mg (0.0625 mmol) and 20.0 g (238.1 mmol) of 4-methylene-2-oxetanone were used.
The reaction was carried out in the same manner as described above, and the title compound (19.3 g, yield 94.2 g) was obtained.
%). The conversion of this reaction was 94.2%, and the catalytic activity was 3580 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 94.0% ee.

[Embodiment 39] [Ru-I _1.5 -{(S) -SEGPHOS)}
Production of ₂ (OTf): After replacing 80 ml of Schlenk tube with nitrogen, 0.5 g (0.51 mmol) of [RuI ₂ (p-cymene)] ₂ was added.
0.63 mg (1.03 mmol) of (S) -SEGPHOS, degassed DMF
Was added and stirred at 75 ° C. for 16 hours. Then, after cooling to 40 ° C. and collecting DMF, 88 mg of NaOTf (0.51
mmol) in 20 ml of methylene chloride and 20 ml of degassed water.
Stirred for hours. Remove the methylene chloride layer with a syringe and remove
After washing with 20 ml and distilling off methylene chloride under reduced pressure, the obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 0.95 title compound
g (94.3% yield) was obtained. FIG. 3 shows the ³¹ P-NMR spectrum of the resulting compound.

Embodiment 40 [Ru-I _1.5 -{(S) -SEGPHOS)}
₂ Production of (OTf): After replacing a 200 ml reaction vessel with nitrogen, [RuI (p-cymene) ｛(S) -SEGPHO
S)] 2.7 g (2.45 mmol) of I and 110 ml of degassed DMF were added.
Stirred at 75 ° C. for 16 hours. Then, after cooling to 40 ° C. and collecting DMF, 0.422 g (2.45 mmol) of NaOTf was added under nitrogen, 20 ml of methylene chloride and 20 ml of degassed water were added, and the mixture was stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure.
It was dried under reduced pressure at 4 ° C for 4 hours. 2.3 g of the title compound (yield
95.0%).

[Example 41] [Ru-I _1.5 -{(S) -SEGPHOS)}
Production of ₂ (OTf): After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmo) of [RuI ₂ (p-cymene)] ₂ was added.
l), 1.26 g (2.06 mmol) of (S) -SEGPHOS, Na
0.36 g (2.09 mmol) of OTf and 40 ml of degassed DMF were added.
Stirred at C for 16 hours. Thereafter, the mixture was cooled to 40 ° C., and after collecting DMF under reduced pressure, 20 ml of methylene chloride and 20 ml of degassed water were added under nitrogen, followed by stirring for 10 minutes. Take the methylene chloride layer with a syringe,
After washing with 20 ml of degassed water and distilling off methylene chloride under reduced pressure, the obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. Title compound
1.9 g (94.3% yield) was obtained.

[Example 42] [Ru-I _1.5 -{(S) -SEGPHOS)}
₂ Production of (OTf): After replacing a 200 ml reaction vessel with nitrogen, [RuI (p-cymene) ｛(S) -SEGPHO
S)] I 2.7 g (2.45 mmol), NaOTf 0.421 g
(2.45 mmol) and 110 ml of degassed DMF were added and stirred at 75 ° C. for 16 hours. Then, after cooling to 40 ° C. and collecting DMF, 20 ml of methylene chloride and 20 ml of degassed water were added under nitrogen, followed by stirring for 30 minutes. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 2.2 g of the title compound (90.9 yield)
%).

[Example 43] [Ru-I _1.5 -{(S) -SEGPHOS)}
Production of ₂ (PF ₆ ): After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmo) of [RuI ₂ (p-cymene)] ₂ was added.
l), 1.26 g (2.06 mmol) of (S) -SEGPHOS, degassed
40 ml of DMF was added and the mixture was stirred at 75 ° C. for 16 hours. Then 40 ° C
After collecting the cooled DMF until the NH ₄ PF ₆ under nitrogen 0.17
1 g (1.02 mmol), methylene chloride (20 ml) and degassed water (20 ml) were added and the mixture was stirred for 16 hours. Take the methylene chloride layer with a syringe,
After washing with 20 ml of degassed water and distilling off methylene chloride under reduced pressure, the obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. Title compound
2.0 g (99.7% yield) was obtained.

[Example 44] [Ru-I _1.5 -{(S) -SEGPHOS)}
Production of ₂ (OTs): After replacing a 80 ml Schlenk tube with nitrogen, 1.0 g (1.02 mmol) of [RuI ₂ (p-cymene)] ₂ was added.
1.26 g (2.06 mmol) of (S) -SEGPHOS, degassed DMF
Was added and stirred at 75 ° C. for 16 hours. After cooling to 40 ° C and collecting DMF, 0.404 g of NaOTs was added under nitrogen.
(2.08 mmol), 20 ml of methylene chloride and 20 ml of degassed water were added, and the mixture was stirred for 16 hours. The methylene chloride layer was removed with a syringe, washed with 20 ml of degassed water, and methylene chloride was distilled off under reduced pressure. The obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. Title compound 2.
03 g (98.5% yield) was obtained.

[Example 45] [Ru-I _1.5 -{(S) -SEGPHOS)}
Production of ₂ (OMs): After replacing 80 ml of Schlenk tube with nitrogen, 1.0 g (1.02 mmo) of [RuI ₂ (p-cymene)] ₂ was added.
l), 1.26 g (2.06 mmol) of (S) -SEGPHOS, degassed
40 ml of DMF was added and the mixture was stirred at 75 ° C. for 16 hours. Then 40 ° C
After cooling to recover DMF, 0.247 g of NaOMs was added under nitrogen.
(2.09 mmol), 20 ml of methylene chloride and 20 ml of degassed water were added, and the mixture was stirred for 16 hours. Take the methylene chloride layer with a syringe,
After washing with 20 ml of degassed water and distilling off methylene chloride under reduced pressure, the obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. Title compound
1.8 g (94.5% yield) was obtained.

Example 46 [Ru-I _1.5 -{(S) -SEGPHOS)}
Production of ₂ {OS (O) ₂ C ₄ F ₉ }: After replacing 80 ml of Schlenk tube with nitrogen, [RuI ₂ (p-cymene)] ₂ was added.
1.2 g (1.23 mmol), 1.51 g of (S) -SEGPHOS
(2.47 mmol), 0.47 g of KOS (O) ₂ C ₄ F ₉ (1.39 m
mol), 36 ml of degassed DMF was added, and the mixture was stirred at 75 ° C for 16 hours.
Thereafter, the mixture was cooled to 40 ° C., and after collecting DMF under reduced pressure, 30 ml of methylene chloride and 30 ml of degassed water were added under nitrogen, followed by stirring for 10 minutes. The methylene chloride layer was removed with a syringe, washed with 30 ml of degassed water, and methylene chloride was distilled off under reduced pressure.
It was dried under reduced pressure at 4 ° C for 4 hours. 3.09 g of the title compound (yield 11
9.4%).

[Example 47] [Ru-I _1.5 -{(S) -SEGPHOS)}
Production of ₂ {OS (O) ₂ C ₈ F ₁₇ }: After replacing 80 ml of Schlenk tube with nitrogen, [RuI ₂ (p-cymene)] ₂ was added.
0.304 g (0.311 mmol), 0.389 of (S) -SEGPHOS
g (0.638 mmol), 0.191 g of KOS (O) ₂ C ₈ F ₁₇
(0.355 mmol) and 10 ml of degassed DMF were added, and the mixture was stirred at 75 ° C for 16 hours. After cooling to 40 ° C and collecting DMF under reduced pressure,
Under nitrogen, 20 ml of methylene chloride and 10 ml of degassed water were added, and the mixture was stirred for 10 minutes. Remove the methylene chloride layer with a syringe and remove
After washing with ml and distilling off methylene chloride under reduced pressure, the obtained complex was dried under reduced pressure at 30 ° C. for 4 hours. 0.87 g of the title compound
(121.6% yield).

Example 48 Production of (R) -4-methyl-2-oxetanone: 500 ml
In a stainless steel autoclave of capacity, under nitrogen atmosphere,
[Ru-I _1.5 -{(S) -SEGPHOS)}
₂ (OTf) 33.59 g (0.034 mmol), 4-methylene-
20.55 g (244.6 mmol) of 2-oxetanone, 80 ml of tetrahydrofuran and 0.45 g of degassed water were charged, and the hydrogen pressure was 50 kgc.
The mixture was stirred at m ³ and a reaction temperature of 50 ° C. for 15 hours. The obtained reaction solution was distilled using a Claisen tube distillation apparatus, and the boiling point was 71 to 73 ° C.
19.1 g (90.8% yield) of a / 29 mmHg fraction was obtained. The conversion of this reaction was 90.8%, and the catalytic activity was 6530 in turnover number. The product was confirmed to be 4-methyl-2-oxetanone as a result of comparative analysis with a sample by gas chromatography, and it was confirmed that the product was an optically active column manufactured by ASTEC (Chiralde).
x G-TA 30m) from gas chromatography (GC) measurement confirmed that the absolute configuration was (R) and the optical purity was 94.5% ee.

Example 49 Production of (R) -4-methyl-2-oxetanone: [Ru
-I _1.5 -{(S) -SEGPHOS)}] ₂ (P
The reaction was carried out in the same manner as in Example 48 except that 35.84 mg (0.0368 mmol) of F ₆ ) and 20.38 g (242.62 mmol) of 4-methylene-2-oxetanone were used to obtain 13.7 g of the title compound (yield: 6).
5.6%). The conversion of this reaction was 65.6%, and the catalytic activity was 4,320 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 95.5% ee.

Example 50 Production of (R) -4-methyl-2-oxetanone [Ru
-I _1.5 -{(S) -SEGPHOS)}] ₂ (OT
s) Example 4 except that 36.75 mg (0.0364 mmol) and 20.0 g (238.1 mmol) of 4-methylene-2-oxetanone were used.
The reaction was carried out in the same manner as in Example 8, and the title compound (13.88 g, yield 67.7) was obtained.
8%). The conversion of this reaction was 68.79% and the catalytic activity was 4500 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 95.6% ee.

Example 51 Production of (R) -4-methyl-2-oxetanone [Ru
-I _1.5 -{(S) -SEGPHOS)}] ₂ (OM
s) The reaction was carried out in the same manner as in Example 48 except that 33.98 mg (0.0364 mmol) and 20.42 mg (243.1 mmol) of 4-methylene-2-oxetanone were used to obtain 14.55 g of the title compound (yield: 6).
9.6%). The conversion of this reaction was 69.6%, and the catalytic activity was 4,650 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 94.8% ee.

Example 52 Production of (R) -4-methyl-2-oxetanone: [Ru
-I _1.5 -{(S) -SEGPHOS)}] ₂ (ClO
₄ ) The reaction was conducted in the same manner as in Example 48 except that 44.65 mg (0.0476 mmol) and 20.29 mg (241.55 mmol) of 4-methylene-2-oxetanone were used to obtain 17.59 g (yield: 84.7%) of the title compound. Was. The conversion of this reaction was 84.7%, and the catalytic activity was 4,300 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 95.4% ee.

Example 53 Production of (R) -4-methyl-2-oxetanone: [Ru
−I _1.5 − {(S) -SEGPHOS)}] ₂ ｛OS
(O) ₂ C ₄ F ₉ ｝ 25.0 mg (0.0238 mmol) and 4-methylene-2-oxetanone 20.34 mg (242.1 mmol) were stirred at a hydrogen pressure of 40 kg / cm ² and a reaction temperature of 60 ° C. for 15 hours. The reaction was conducted in the same manner as in Example 48, and the title compound (18.9) was obtained.
9 g (91.2% yield) was obtained. The conversion of this reaction is 100
%, Catalytic activity was 10180 turnovers. The absolute configuration of the product was (R) -form and the optical purity was 94.4% ee.

Example 54 Production of (R) -4-methyl-2-oxetanone: [Ru
−I _1.5 − {(S) -SEGPHOS)}] ₂ ｛OS
(O) ₂ C ₈ F ₁₇ ｝ 22.85 mg (0.0198 mmol) and 4-methylene-2-oxetanone 20.54 g (244.5 mmol) were used.
The reaction was carried out in the same manner as in Example 48 except that the mixture was stirred at a hydrogen pressure of 40 kg / cm ² and a reaction temperature of 60 ° C. for 15 hours, thereby obtaining 18.45 g of the title compound
(87.7% yield). The conversion of this reaction was 87.7%, and the catalyst activity was 10830. The absolute configuration of the product was (R) -form and the optical purity was 93.8% ee.

Comparative Example 1 Production of (R) -4-methyl-2-oxetanone: Ruthenium described in JP-A-7-206885
An iodo-optically active phosphine complex was produced, and this was used as a catalyst to produce optically active 4-methyl-2-oxetanone. That is, Ru ₂ Cl ₄ [(S) -T-BINA was added to a 300 ml reaction vessel which had been purged with nitrogen in advance.
P] ₂ NEt ₃ 0.57 g (0.632 mmol), NaI 0.95 g
(6.34 mmol)), (C ₄ H ₉ ) ₄ NBr 2.0 mg (0.0
063 mmol), methylene chloride (50 ml) and distilled water (20 ml) were added, and the mixture was stirred at room temperature for 44 hours. After the reaction, the methylene chloride layer was collected with a syringe, methylene chloride was distilled off under reduced pressure, and the obtained complex was dried under reduced pressure at 50 ° C. for 4 hours to obtain Ru-I-.
0.65 g of [(S) -T-BINAP] was obtained. This complex R
uI-[(S) -T-BINAP] 82.0 mg (0.0794 m
mol), 20.1 g of 4-methylene-2-oxetanone (239.3
The reaction was carried out in the same manner as in Example 12 except that (mmol) was used to obtain 10.0 g (yield: 48.8%) of the title compound. The conversion of this reaction was 50.0%, and the catalytic activity was 15% in turnover.
00. The absolute configuration of the product is the (R) form and the optical purity is
93.4% ee.

Comparative Example 2 Production of (R) -4-methyl-2-oxetanone: [Ru
I (p-cymene) ((S) -T-BINAP)]
Example 1 except that 139. mg (0.119 mmol) of I and 20.0 g (238.1 mmol) of 4-methylene-2-oxetanone were used.
Reaction was carried out in the same manner as in Example 2 to give 9.50 g of the title compound (yield 47.5 g).
%). The conversion of this reaction was 48.0%, and the catalytic activity was 960 in turnover number. The absolute configuration of the product was (R) -form and the optical purity was 92.8% ee.

Comparative Example 3 Production of (R) -4-methyl-2-oxetanone: Ru
(CH ₃ COO) ₂ [(S) -T-BINAP] 215.5
mg (0.238 mmol), 4-methylene-2-oxetanone 20.
The reaction was carried out in the same manner as in Example 12 except that 0 g (238.1 mmol) was used to obtain 11.0 g (yield: 55.0%) of the title compound. The conversion of this reaction was 56.6% and the catalytic activity was turn-on.
It was 570 at the bar. The absolute configuration of the product was (R) -form and the optical purity was 93.6% ee.

Embodiments 12 to 19, 31 to 38, 46
To 50 and Comparative Examples 1 to 3 (turnover)
) And the steric configuration and optical purity (% ee) of the obtained 4-methyl-2-oxetanone are summarized in Table 1.

[0152]

[Table 1]

From the above results, the ruthenium-iodo-optically active phosphine complex of the present invention [Ru- (I) _q- (T
¹ ) _n (L)] _m (T ² ) _p can be used as a catalyst to promote the reaction at a much higher rate than the conventionally known ruthenium-optically active phosphine complex. It is also clear that high optical purity products can be obtained.

[0154]

The ruthenium-iodine-optically active phosphine complex obtained by the process of the present invention has an extremely high catalytic activity and a high asymmetric yield in an asymmetric reaction.
That is, since a product with high optical purity can be obtained, it can be widely used as an economically advantageous catalyst for asymmetric synthesis. In particular, by using this complex as a catalyst to asymmetrically hydrogenate 4-methylene-2-oxetanone, the optical activity 4 useful as a polymer material or the like is obtained.
-Methyl-2-oxetanone can be efficiently obtained in a short time and at a high optical purity.

[Brief description of the drawings]

FIG. 1 is a diagram showing the entire LC mass spectrum of the product of Example 20.

FIG. 2 shows the molecular weight of the LC mass spectrum of FIG.
It is an enlarged view of the part of 2030.

FIG. 3 [Ru-I _1.5 -｛(S)-] obtained in Example 39
FIG. 3 is a diagram showing a ³¹ P-NMR spectrum of (SEGPHOS)}] ₂ (OTf).

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Toshimitsu Hagiwara 1-4-11 Nishi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Takasago International Corporation

Claims (11)

[Claims] (1) Formula (1) [Ru- (I) _q- (T ¹ ) _n (L)] _m (T ² ) _p (1) wherein L is optical activity A bidentate phosphine ligand, T ¹ is a carboxylate anion, T ² is a halogen atom, an anion excluding a carboxylate anion, n is 0 to 1, m is 1 to 3, p is 0 to 1, and q is 1 Or 1 to 1.5 when m is 2), a ruthenium-iodo optically active bidentate phosphine complex represented by the formula: 2. The optically active bidentate phosphine ligand L is represented by the formula (2): (Hereinafter sometimes referred to as R ¹ over BIPH in. Formula, R ¹
Is a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, an aryl group which may have a substituent selected from the group consisting of a lower alkylamino group having 1 to 4 carbon atoms and a halogen atom. Or a cycloalkyl group having 3 to 8 carbon atoms, R ² and R ³ may be the same or different and each may be a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, or R ²
And R ³ together represent a group which may form a 5- or 6-membered ring). The optically active ruthenium-iodo bidentate phosphine according to claim 1, wherein Complex. 3. Formula (3) [RuI (arene) (L)] I (3) wherein arene is a hydrocarbon having a benzene ring, L
Ruthenium is expressed by showing the optically active bidentate phosphine ligand of claim 1 wherein) - optically active phosphine complex of formula ^{(4) (T 1) aZ} 1 ··· (4) ( wherein, Z ¹ Represents an alkali metal or an alkaline earth metal, a represents ¹ when Z ¹ is an alkali metal, 2 represents when Z ¹ is an alkaline earth metal, and T ¹ is defined as the formula (1) according to claim 1. A) a carboxylate represented by the same formula or a formula (5) Z ² b (T ² ) c (5) (wherein Z ² is a mono- or di-cation such as an alkali metal, an alkaline earth metal, and ammonium) And T ² represents a mono- or dianion other than a halogen atom and a carboxylic acid, b and c are 1 when Z ² is a monocation and T ² is a mono-anion, and Z ² is When T ² is a dianion in the case of monocations, b is 2
And c is 1; b and c are 1 when Z ² is a dication and T ² is a dianion; and when Z ² is a dication and T ² is a monoanion. b
3. The method for producing an optically active ruthenium-iodo bidentate phosphine complex according to claim 1 or 2, wherein a salt represented by the formula (1) and c represents 2) is reacted in a polar solvent. 4. The same definition as in formula (1) represented by formula (6) [RuI ₂ (arene)] ₂ ... (6) wherein arene represents a hydrocarbon having a benzene ring. And an optically active bidentate phosphine ligand of the formula (4) (T ¹ ) aZ ¹ ... (4) wherein Z ¹ , a and T ¹ are the same as defined in the formula (4) according to claim 3. A carboxylate represented by the same formula) or a formula (5) Z ² b (T ² ) c (5) (where Z ² , b, T ² , and c are the formula (5) )
3. The method for producing an optically active ruthenium-iodo bidentate phosphine complex according to claim 1 or 2, wherein the salt represented by the formula (1) is reacted in a polar solvent. 5. The ruthenium-iodo according to claim 1 or 2.
A process for producing optically active 4-methyl-2-oxetanone, comprising asymmetrically hydrogenating 4-methylene-2-oxetanone using a de-optically active bidentate phosphine complex as a catalyst. 6. An optically active bidentate phosphine ligand L represented by the formula (7) wherein R ² and R ^{3 in} the formula (2) together form a 6-membered benzene ring (R ¹ -BINAP) Embedded image (Where R ¹ has a substituent selected from the group consisting of a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a lower alkylamino group having 1 to 4 carbon atoms, and a halogen atom. Aryl group or 3 carbon atoms
Wherein R ² and R ³ of the formula (2) together with an optically active tertiary phosphine represented by the following formulas (8) to (8) represent a cycloalkyl group of 6 members: H ⁸ -R ¹ over BINA
P) (Wherein, R ¹ has a substituent selected from the group consisting of a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a lower alkylamino group having 1 to 4 carbon atoms, and a halogen atom. Aryl group or carbon number 3
And R ² and R ³ of the formula (2) together form an optically active tertiary phosphine represented by the following formula:
Formula (9) having a dioxolane ring (R ¹ -SEGP)
HOS) (Wherein, R ¹ has a substituent selected from the group consisting of a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a lower alkylamino group having 1 to 4 carbon atoms, and a halogen atom. Aryl group or carbon number 3
3 to 8), wherein the compound is one selected from optically active tertiary phosphines represented by the following formulas (1) to (3). 7. The method for producing optically active 4-methyl-2-oxetanone according to claim 5, wherein the ruthenium-iodine-optically active phosphine complex according to claim 6 is used as a catalyst. 8. [RuI (arene) (R ¹ -BINAP)] I (10) wherein arene is a hydrocarbon having a benzene ring, R
^1- BINAP represents a ruthenium-iodo complex represented by the formula (7)) and a formula (4) (T ¹ ) aZ ¹ ... (4) (wherein Z ¹ , a and T ¹ are claims) (5) Z ² b (T ² ) c (5) wherein Z ² , b, T ² , c is the expression (5) according to claim 3
Wherein the salt represented by the formula (1) is reacted in a polar solvent.
Preparation of de-optically active bidentate phosphine complexes. 9. A ruthenium-iodo complex represented by the formula (6) [RuI ₂ (arene)] ₂ ... (6) wherein arene represents a hydrocarbon having a benzene ring, and R ^1- BIN
The ruthenium-iodide according to claim 4, wherein the optically active phosphine represented by AP is reacted with the salt represented by the formula (4) or (5) in a polar solvent.
A method for producing an optically active bidentate phosphine complex. 10. A compound represented by the formula (11): [RuI (arene) (R ¹ -SEGPHOS)] I (11) wherein arene is a hydrocarbon having a benzene ring, R
¹ -SEGPHOS is the same as defined in the formula (9) of claim 6), wherein a ruthenium-optically active tertiary phosphine complex represented by the formula (5) is reacted with a salt represented by the formula (5) in a polar solvent. The ruthenium-yo- according to claim 3,
Preparation of de-optically active bidentate phosphine complexes. 11. A ruthenium complex represented by the formula (6) [RuI ₂ (arene)] ₂ ... (6), wherein arene represents a hydrocarbon having a benzene ring, and R ¹ -SEGPHOS.
5. The method according to claim 4, wherein the optically active phosphine represented by the formula (9) is reacted with the salt represented by the formula (5) in a polar solvent. For producing a ruthenium-iodine-optically active phosphine complex of