JP6521373B2 - Phosphine-Olefin Ligands Having Planar Asymmetric Cyclopentadienyl-Manganese Complexes in the Basic Framework - Google Patents

Description

  The present invention relates to a phosphine-olefin ligand having a plane asymmetric cyclopentadienyl-manganese complex in a basic skeleton, a method of using the same, a catalyst composition containing the same, and a method of manufacturing the same.

  Many physiologically active substances, particularly pharmaceuticals, have compounds having asymmetric centers, and compounds having these asymmetric centers have optical isomers. The absolute configuration of the asymmetric center is extremely important, with one of the enantiomers having efficacy, and the other enantiomer may be ineffective or deleterious.

As a method of selectively obtaining one of the optically active enantiomers of such optical isomers, optical resolution of enantiomers, asymmetric synthesis reaction, diastereodifferentiation reaction using an asymmetric auxiliary agent, enantio differentiation using an asymmetric catalyst Asymmetric synthesis such as reaction is used.
The above asymmetry includes element-centred asymmetry, axial asymmetry (atrope isomer), helicity and plane asymmetry.

Among others, the present inventors recently focused on asymmetric synthesis using planar asymmetry and are shown below:
A six-membered ring (η ⁶ -arene) -P-chromium dicarbonyl complex was successfully prepared.
The (η ⁶ -arene) -P-chromium dicarbonyl complex described above has a plane asymmetric (π-arene) chromium dicarbonyl skeleton and is a phosphine-olefin ligand that is a novel P-olefin ligand having an optical purity of It has been found that it is possible to obtain a substantially pure high enantiomeric excess (hereinafter referred to as ee) (Non-patent Document 1).

M. Ogasawara, Y-Y. Tseng, S. Arae, T. Morita, T. Nakaya, W. Y. Wu, T. Takahashi and K. Kamikawa, J. Am. Chem. Soc. 2014, 136, 9377-9384.

However, for the cyclic enone compounds such as 2-cyclohexenone, the above-mentioned P-olefin ligands give rise to 1,4-adducts having high yield and optical purity, but for aliphatic enone compounds Also had the knowledge that the yield and the optical purity were not so high.
Therefore, the present inventors are not only cyclic enone compounds but also various enone compounds including aliphatic enone compounds, which are high in yield and optical purity as asymmetric ligands for transition metal catalyzed asymmetric reactions. Make provision an issue.

As a result of various investigations, the present inventors compared five-membered ring (η ⁵ -cyclopentadienyl) -P-manganese with the above-mentioned six-membered ring (η ⁶ -arene) -P-chromium dicarbonyl complex. The inventors have found that the dicarbonyl complex functions as an extremely excellent transition metal 1,4-addition asymmetric reaction surface asymmetric ligand, and have completed the present invention.

Thus, according to the invention, the following general formula (7):
(7)
(Wherein R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group, and R ′ is optionally substituted with a hydrogen atom or an aryl group be optionally substituted with or unprotected _C 1 -C ₄ alkyl or _C 1 -C ₄ alkyl group is an aryl group, R _"is, C 1 -C ₄ alkyl or _C 1 -C ₄ An aryl group which may be optionally substituted with an alkyl group)
(+) Or (−)-((( ⁵ 1-phosphino-2-propenyl) cyclopentadienyl-P) manganese (I) dicarbonyl compound represented by

  Further, according to the present invention, in the general formula (7), R is an isopropyl group, a phenyl group or a 3,5-xylyl group, and R 'is a hydrogen atom, a methyl group, an isopropyl group, a phenyl group or There is provided the aforementioned compound, wherein R is a benzyl group, and said R ′ ′ is an isopropyl group, a phenyl group or a 3,5-xylyl group.

  Further, according to the present invention, in the general formula (7), R is a phenyl group or 3,5-xylyl group, R ′ is a methyl group or isopropyl group, and R ′ ′ is a phenyl group or 3,5 Provided is a compound as described above which is -xylyl.

Furthermore, according to the present invention, the above equation (7):
(7)
(Wherein R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group, and R ′ is optionally substituted with a hydrogen atom or an aryl group be optionally substituted with or unprotected _C 1 -C ₄ alkyl or _C 1 -C ₄ alkyl group is an aryl group, R _"is, C 1 -C ₄ alkyl or _C 1 -C ₄ An aryl group which may be optionally substituted with an alkyl group)
In represented by, (+) or (-) - a catalytic amount of ((eta ^{5-1-phosphino-2-propenyl)} cyclopentadienyl -P) manganese (I) dicarbonyl compounds, transition metal catalyzed asymmetric There is provided a method of using the compound of formula (7) as a planar asymmetric ligand for transition metal catalyzed asymmetric reactions characterized in that it is used in a reaction.

  The transition metal catalyzed asymmetric reaction is a transition metal catalyzed asymmetric allylic amination, asymmetric allylic thioetherification, asymmetric allylic alkynylation or asymmetric Suzuki-Miyaura cross coupling reaction; Asymmetric 1,4-addition reaction of organoboronic acid to enone compounds or asymmetric 1,2-addition reaction to imine compounds; Asymmetric 1,4-addition reaction of organozinc compounds to enone compounds or imine An asymmetric 1,2-addition reaction to a compound; or an asymmetric 1,4-addition reaction to an enone compound or an asymmetric 1,2-addition reaction to an imine compound as described above. Methods of use as asymmetric ligands for reactions are provided.

  Also according to the invention there is provided the use as described above wherein said transition metal catalyst is rhodium, palladium or iridium.

Moreover, the general formula according to the present invention of (7) (+) or (-) - and ((eta ^{5-1-phosphino-2-propenyl)} cyclopentadienyl -P) manganese (I) dicarbonyl compound A catalyst composition comprising a transition metal salt or transition metal complex precursor is provided.

Furthermore, according to the invention, the following formula (1):
(1)
The lithiation agent and the brominating agent are reacted with cyclopentadienyl manganese tricarbonyl (1) represented by the formula (2) in an aprotic organic solvent,

(2)
An η ⁵ -bromocyclopentadienyl manganese (I) tricarbonyl compound represented by the formula is obtained, which is reacted with lithium amide and dimethylformamide in an aprotic organic solvent to obtain a compound of the formula (3):

(3)
In represented (±) - give (eta ^{5-1-bromo-2-formyl-cyclopentadienyl)} manganese (I) tricarbonyl compound in an aprotic organic solvent thereto, methyl iodide triphenylphosphonium and The organic base is reacted, and the formula (4):

(4)
In represented (±) - give (eta ^{5-1-bromo-2-vinyl-cyclopentadienyl)} manganese (I) tricarbonyl compound, in benzene to the following formula:

(Wherein, R 'represents a hydrogen atom, optionally substituted by C ₁ optionally -C ₄ alkyl or C ₁ -C ₄ alkyl optionally substituted in the aryl group with a group with an aryl group , R ′ ′ is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group)
The allyl phosphine compound represented by is reacted under light irradiation using a mercury lamp as a light source, and the formula (5):

(5)
(Wherein, R 'represents a hydrogen atom, optionally substituted by C ₁ optionally -C ₄ alkyl or C ₁ -C ₄ alkyl optionally substituted in the aryl group with a group with an aryl group , R ′ ′ is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group)
In represented (±) - give (eta ^{5-1-bromo-2-vinyl-cyclopentadienyl)} allyl phosphine manganese (I) dicarbonyl compounds, which under inert gas, aprotic organic solvent metathesis By the olefin metathesis reaction in the presence of a catalyst, formula (6):

(6)
(Wherein, R 'represents a hydrogen atom, optionally substituted by C ₁ optionally -C ₄ alkyl or C ₁ -C ₄ alkyl optionally substituted in the aryl group with a group with an aryl group , R ′ ′ is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group)
In represented (±) - give (eta ^5-1-bromo-2- (3-phosphino-1-propenyl) cyclopentadienyl -P) manganese (I) dicarbonyl compounds,

This is optically resolved by HPLC for optical resolution,
(+) - (eta ^5-1-bromo-2- (3-phosphino-1-propenyl) cyclopentadienyl -P) manganese (I) dicarbonyl compounds, and (-) - (eta ^5-1-bromo -2- (3-Phosphino-1-propenyl) cyclopentadienyl-P) manganese (I) dicarbonyl compounds are obtained, which, in an aprotic organic solvent,
R ₂ PCl
(Wherein, R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group)
Are each reacted to give formula (7):

(7)
(Wherein R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group, and R ′ is optionally substituted with a hydrogen atom or an aryl group be optionally substituted with or unprotected _C 1 -C ₄ alkyl or _C 1 -C ₄ alkyl group is an aryl group, R _"is, C 1 -C ₄ alkyl or _C 1 -C ₄ An aryl group which may be optionally substituted with an alkyl group)
In represented by, (+) or (-) - method for producing ((eta ^{5-1-phosphino-2-propenyl)} cyclopentadienyl -P) manganese (I) dicarbonyl compound.

Furthermore, according to the invention, the aprotic organic solvent is tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride or tetrachloroethane.
The above-mentioned lithiation agent is lower alkyllithium such as n-butyllithium, s-butyllithium and t-butyllithium or lithium diisopropylamide, lithium 2,2,6,6-tetramethylpiperidide and lithium Lithium amide such as hexamethyldisilazide,
The brominating agent is triphenylphosphine dibromide, dioxane dibromide, sodium bromide, bromotrichloromethane, 1,2-dibromotetrachloroethane or dimethylbromosulfonium bromide.
The organic base is a C _{1 to} C ₅ lower alkyl or alkoxide compound of an alkali metal, triethylamine, pyridine, dimethylaminopyridine, quinoline, piperidine or diazabicycloundecene,
The method according to the above, wherein the metathesis catalyst is a first generation Grubbs catalyst, a second generation Grubbs catalyst, a first generation Huberder-Grubbs catalyst, or a second generation Huberder-Grubbs catalyst.

According to the present invention, the transition metal catalyzed asymmetric reaction surfaces chiral ligand, (+) or (-) - ((eta ^{5-1-phosphino-2-propenyl)} cyclopentadienyl -P) Manganese (I) A dicarbonyl compound can be provided.
Of the present invention (+) or (-) - a ((eta ^{5-1-phosphino-2-propenyl)} cyclopentadienyl -P) manganese (I) dicarbonyl compound, transition metal salt or transition metal complex precursor, In particular, by using a rhodium complex together with a rhodium complex as a catalyst composition, it is possible to produce a 1,4-adduct with high optical purity and high yield not only for cyclic enone compounds but also for aliphatic enone compounds.

It is a < ¹ > H-NMR spectrum of compound 6 'obtained by the reference manufacture example 1. FIG. It is a ¹³ C-NMR spectrum of compound 6 ′ obtained in Reference Production Example 1. It is a < ¹ > H-NMR spectrum of compound 1b 'obtained by the reference manufacture example 2-b. It is a ¹³ C-NMR spectrum of compound 1b ′ obtained in Reference Production Example 2-b. It is a < ³¹ > P-NMR spectrum of compound 1b 'obtained by the reference manufacture example 2-b. It is a < ¹ > H-NMR spectrum of compound 1c 'obtained by the reference manufacture example 2-c. It is a ¹³ C-NMR spectrum of compound 1c 'obtained in Reference Production Example 2-c. It is a < ³¹ > P-NMR spectrum of compound 1c 'obtained by the reference manufacture example 2-c. It is a < ¹ > H-NMR spectrum of compound 1 d 'obtained by the reference manufacture example 2-d. It is a < ¹³ > C-NMR spectrum of compound 1 d 'obtained in Reference Production Example 2-d. It is a < ³¹ > P-NMR spectrum of compound 1 d 'obtained by the reference manufacture example 2-d. It is a < ¹ > H-NMR spectrum of compound ¹ e 'obtained by the reference manufacture example 2-e. It is a < ¹³ > C-NMR spectrum of compound 1 e 'obtained in Reference Production Example 2-e. It is a < ³¹ > P-NMR spectrum of compound 1 e 'obtained by the reference manufacture example 2-e. It is a < ¹ > H-NMR spectrum of compound ¹ f 'obtained by the reference manufacture example 2-f. It is a < ¹³ > C-NMR spectrum of compound 1 f 'obtained in Reference Production Example 2-f. It is a < ³¹ > P-NMR spectrum of compound 1 f 'obtained by the reference manufacture example 2-f. It is a < ¹ > H-NMR spectrum of compound 2b 'obtained by the reference manufacture example 3-b. It is a ¹³ C-NMR spectrum of compound 2b ′ obtained in Reference Production Example 3-b. It is a < ³¹ > P-NMR spectrum of compound 2b 'obtained by the reference manufacture example 3-b. It is a < ¹ > H-NMR spectrum of compound 2c 'obtained by the reference manufacture example 3-c. It is a < ¹³ > C-NMR spectrum of compound 2c 'obtained by the reference manufacture example 3-c. It is a < ³¹ > P-NMR spectrum of compound 2c 'obtained by the reference manufacture example 3-c. It is a < ¹ > H-NMR spectrum of compound 2 d 'obtained by the reference manufacture example 3-d. It is a < ¹³ > C-NMR spectrum of compound 2 d 'obtained in Reference Production Example 3-d. It is a < ³¹ > P-NMR spectrum of compound 2d 'obtained by the reference manufacture example 3-d. It is a < ¹ > H-NMR spectrum of compound 2e 'obtained by the reference manufacture example 3-e. It is a ¹³ C-NMR spectrum of compound 2e ′ obtained in Reference Production Example 3-e. It is a < ³¹ > P-NMR spectrum of compound 2e 'obtained by the reference manufacture example 3-e. It is a < ¹ > H-NMR spectrum of compound 2 f 'obtained by the reference manufacture example 3-f. It is a < ¹³ > C-NMR spectrum of compound 2 f 'obtained in Reference Production Example 3-f. It is a < ³¹ > P-NMR spectrum of compound 2 f 'obtained in Reference Production Example 3-f. It is a < ¹ > H-NMR spectrum of compound 3b 'obtained by the reference manufacture example 4-b. It is a ¹³ C-NMR spectrum of compound 3b 'obtained in Reference Production Example 4-b. It is a < ³¹ > P-NMR spectrum of compound 3b 'obtained by the reference manufacture example 4-b. It is a < ¹ > H-NMR spectrum of compound 3c 'obtained by the reference manufacture example 4-c. It is a ¹³ C-NMR spectrum of compound 3c 'obtained in Reference Production Example 4-c. It is a < ³¹ > P-NMR spectrum of compound 3c 'obtained by the reference manufacture example 4-c. It is a < ¹ > H-NMR spectrum of compound 3d 'obtained by the reference manufacture example 4-d. It is a ¹³ C-NMR spectrum of compound 3d ′ obtained in Reference Production Example 4-d. It is a < ³¹ > P-NMR spectrum of compound 3d 'obtained by the reference manufacture example 4-d. It is a < ¹ > H-NMR spectrum of compound 3e 'obtained by the reference manufacture example 4-e. It is a < ¹³ > C-NMR spectrum of compound 3e 'obtained in Reference Production Example 4-e. It is a < ³¹ > P-NMR spectrum of compound 3e 'obtained by the reference manufacture example 4-e. It is a < ¹ > H-NMR spectrum of compound 3f 'obtained by the reference manufacture example 4-f. It is a < ¹³ > C-NMR spectrum of compound 3 f 'obtained in Reference Production Example 4-f. It is a < ³¹ > P-NMR spectrum of compound 3f 'obtained by the reference manufacture example 4-f. It is a < ¹ > H-NMR spectrum of compound 3g 'obtained by the reference manufacture example 4-g. It is a < ¹³ > C-NMR spectrum of compound 3g 'obtained by the reference manufacture example 4-g. It is a < ³¹ > P-NMR spectrum of compound 3g 'obtained by the reference manufacture example 4-g. It is a < ¹ > H-NMR spectrum of compound 3h 'obtained by the reference manufacture example 4-h. It is a ¹³ C-NMR spectrum of compound 3h ′ obtained in Reference Production Example 4-h. It is a < ³¹ > P-NMR spectrum of compound 3h 'obtained by the reference manufacture example 4-h. It is a < ¹ > H-NMR spectrum of the compound 3 obtained in Example 1-2. It is a < ¹³ > C-NMR spectrum of the compound 3 obtained in Example 1-2. It is a < ¹ > H-NMR spectrum of the compound 4 obtained in Example 1-3. It is a < ¹³ > C-NMR spectrum of the compound 4 obtained in Example 1-3. It is a < ¹ > H-NMR spectrum of the compound 5 obtained in Example 1-4. It is a < ¹³ > C-NMR spectrum of the compound 5 obtained in Example 1-4. It is a < ³¹ > P-NMR spectrum of the compound 5 obtained in Example 1-4. It is a < ¹ > H-NMR spectrum of the compound 6 obtained in Example 1-5. It is a < ¹³ > C-NMR spectrum of the compound 6 obtained in Example 1-5. It is a < ³¹ > P-NMR spectrum of the compound 6 obtained in Example 1-5. It is a < ¹ > H-NMR spectrum of compound 7a obtained in Example 1-7. It is a < ¹³ > C-NMR spectrum of the compound 7a obtained in Example 1-7. It is a < ³¹ > P-NMR spectrum of the compound 7a obtained in Example 1-7. It is a < ¹ > H-NMR spectrum of the compound 7b obtained in Example 1-7. It is a < ¹³ > C-NMR spectrum of the compound 7b obtained in Example 1-7. It is a < ³¹ > P-NMR spectrum of the compound 7b obtained in Example 1-7. 3 is an HPLC chart showing the optical purity of 3- (p-methylphenyl) cyclohexanone obtained in Example 2. 3 is an HPLC chart showing the optical purity of 3- (p-methoxyphenyl) clohexanone obtained in Example 3. 3 is an HPLC chart showing the optical purity of 3- (p-trifluoromethylphenyl) clohexanone obtained in Example 4. 3 is an HPLC chart showing the optical purity of 3- (p-fluorophenyl) chlorhexanone obtained in Example 5. 7 is an HPLC chart showing the optical purity of 3- (o-methylphenyl) cyclohexanone obtained in Example 6. 7 is an HPLC chart showing the optical purity of 4-phenylpentan-2-one obtained in Example 7. 7 is an HPLC chart showing the optical purity of 4-phenylhept-2-one obtained in Example 8. 7 is an HPLC chart showing the optical purity of 4-phenylnon-2-one obtained in Example 9. FIG. 5 is an HPLC chart showing the optical purity of N-[(p-chlorophenyl) phenylmethyl] tosylamide obtained in Comparative Example 1. FIG. FIG. 6 is an HPLC chart showing the optical purity of 3- (p-methylphenyl) cyclohexanone obtained in Comparative Example 2. FIG. FIG. 7 is an HPLC chart showing the optical purity of (R) -3-phenyl-δ-valerolactone and (S) -3-phenyl-δ-valerolactone obtained in Comparative Example 3, respectively. It is an HPLC chart which shows the optical purity of (R) -4- phenyl -3- pentan -2-one and (S) -4- phenyl -3- pentanone obtained in comparative example 4, respectively. FIG. 7 is an HPLC chart showing the optical purity of (R) -4-phenylnon-2-one and (S) -4-phenylnon-2-one obtained in Comparative Example 5, respectively. It is an HPLC chart which shows the optical purity of (R) -N- benzyl -3- phenyl succinimide and (S)-N- benzyl -3- phenyl succinimide which were obtained by comparative example 6, respectively.

In the present invention, the term "planar asymmetry" means that the real image and the mirror image of the mirror image can not be superimposed on each other based on the plane structure (in this case, the aromatic ring surface) contained in the molecule. It refers to molecules having a spatial molecular structure, in which case there is "facial asymmetry" in these molecules.
Specifically, the following formula:
When converting an aromatic compound having a different substituent at the ortho position (or meta position) of the aromatic ring to an arene chromium complex, as shown in the following, from the upper side of the aromatic ring face (direction of (a)) to Cr (CO) _The chromium complex obtained by ₃ and the chromium complex obtained by Cr (CO) ₃ approaching from the lower side (direction of (b)) are mutually enantiomers (molecules in non-superimposable relationship to each other) It is related, and this molecule is said to have "planar asymmetry" derived from the aromatic ring surface.

In the present invention, the term "ligand" is a compound that coordinates to a catalyst metal and has a role of controlling the reactivity in a catalytic reaction.
Further, in the present invention, the term "asymmetric ligand" used in the present invention refers to the central asymmetry, etc., in a reaction in which a central asymmetry or the like newly appears in the molecular structure of the product obtained by the catalytic reaction. It means that in principle, it is possible to control the stereochemistry of That is, generally, when the catalytic metal is coordinated to the reaction substrate, the asymmetric ligand controls the reaction from which the catalytic metal approaches to the reaction substrate to form central asymmetry.
Further, in the present invention, the term "planar asymmetric ligand" means that the molecular structure of the above-mentioned asymmetric ligand necessarily includes an asymmetric element, for example, the asymmetric element As, it means a ligand having a plane asymmetric element.

The present invention relates to the presence of (+) or (-)-(( ⁵ 5-1-phosphino-2-propenyl) cyclopentadienyl-P) manganese (I) dicarbonyl compound as a transition metal salt or transition metal complex precursor The present invention is characterized by the use as a planar asymmetric ligand for transition metal catalyzed asymmetric reactions.

The term "transition metal catalyzed asymmetric reaction" used in the present invention includes transition metal catalyzed asymmetric allylic amination, asymmetric allylic thioetherification, asymmetric allylic alkynylation or asymmetric Suzuki. -Miyaura cross coupling reaction; asymmetric 1,4-addition reaction of organoboronic acid to enone compound or asymmetric 1,2-addition reaction to imine compound; asymmetry of organozinc compound to enone compound 1 4, 4-addition reaction or asymmetric 1,2-addition reaction to imine compound; or asymmetric 1,4-addition reaction of organic titanium compound to enone compound or asymmetric 1,2-addition reaction to imine compound Can be mentioned.
It is also a feature of the present invention that the asymmetric ligand for asymmetric reaction according to the present invention can be advantageously used as the above-mentioned surface ligand for asymmetric reaction.

  In the present invention, the term "transition metal" means rhodium, palladium or iridium used as a catalyst in the above-mentioned asymmetric reaction.

In the present invention, the transition metal complex precursor, the present invention (+) or (-) - ((eta ^{5-1-phosphino-2-propenyl)} cyclopentadienyl -P) manganese (I) dicarbonyl compound (7):
(7)
(Wherein R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group, and R ′ is optionally substituted with a hydrogen atom or an aryl group be optionally substituted with or unprotected _C 1 -C ₄ alkyl or _C 1 -C ₄ alkyl group is an aryl group, R _"is, C 1 -C ₄ alkyl or _C 1 -C ₄ An aryl group which may be optionally substituted with an alkyl group)
Is a compound for providing a transition metal to coordinate to the transition metal.
When the transition metal is rhodium or iridium, the transition metal precursor can be represented by, for example, [MXL] ₂ .
Here, M is Rh ¹ or Ir ¹ and X is a monovalent anionic ligand, for example, Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , OMe ^{− and the} like. L is a zero-valent weak ligand, and examples thereof include olefins such as ethylene and cyclooctene, and dienes such as cyclooctadiene and 2,5-norbornadiene. Specifically, [RhCl (η ² -C ₂ H ₄ ) ₂ ] ₂ , [RhCl (η ² -C ₈ H ₁₄ ) ₂ ] ₂ , [RhCl (cod)] 2, [RhCl (nbd)] ₂ Can be mentioned.
When the transition metal is palladium, examples of the transition metal precursor include Pd (dba) ₂ , [Pdcl (allyl) ₂ ], PdCp (allyl) and the like.

In the present invention, the term "aprotic organic solvent" refers to tetrahydrofuran (THF), dioxane, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethane, cyclohexane, benzene, acetone, dimethyl sulfoxide, acetonitrile, dimethylformamide and the like Can be mentioned.
The preparation of the compounds according to the invention is usually carried out with cooling in an aprotic solvent.

The term "lithiating agent" used in the present invention includes C ₁ -C ₅ lower alkyl lithium or lithium amide, and the lower alkyl lithium includes n-butyllithium, s-butyllithium and t-butyl. Examples of the lithium amide include lithium diisopropylamide, lithium 2,2,6,6-tetramethylpiperidide and lithium hexamethyldisilazide.

  The term "brominating agent" used in the present invention includes triphenylphosphine dibromide, dioxane dibromide, sodium bromide, bromotrichloromethane, 1,2-dibromotetrachloroethane or dimethylbromosulfonium bromide and the like.

The term "organic base" as used in the present invention, lower alkyl or alkali metal alkoxides of C ₁ -C _5, especially Li, or include compounds of the Na or K, or triethylamine, pyridine, dimethylaminopyridine, Amine bases such as quinoline, piperidine or diazabicycloundecene can be mentioned.

  As the term "metathesis catalyst" used in the present invention, first generation Grubbs catalyst (also referred to as Grubbs I catalyst), second generation Grubbs catalyst (also referred to as Grubbs II catalyst), first generation Hoveyer-Grubbs catalyst (Hoveyer-Grubbs catalyst) And the second generation Hoveider-Grubbs catalysts (also called Hoveir-Grubbs II catalysts).

  For the preparation of the compound according to the present invention, an appropriate selection may be used from the examples of the aprotic organic solvent, the lithiation agent, the brominating agent, the organic salt or the metathesis catalyst described above.

The asymmetric ligand for transition metal complex formation according to the present invention has the following formula (7):
(Wherein R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group, and R ′ is optionally substituted with a hydrogen atom or an aryl group be optionally substituted with or unprotected _C 1 -C ₄ alkyl or _C 1 -C ₄ alkyl group is an aryl group, R _"is, C 1 -C ₄ alkyl or _C 1 -C ₄ An aryl group which may be optionally substituted with an alkyl group)
The (+) or (−)-((η ⁵ 1-phosphino-2-propenyl) cyclopentadienyl-P) manganese (I) dicarbonyl compound (7), which can be represented by It can also be obtained and isolated according to the following synthesis scheme 1.

(Wherein R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group, and R ′ is optionally substituted with a hydrogen atom or an aryl group be optionally substituted with or unprotected _C 1 -C ₄ alkyl or _C 1 -C ₄ alkyl group is an aryl group, R _"is, C 1 -C ₄ alkyl or _C 1 -C ₄ An aryl group which may be optionally substituted with an alkyl group).

That is, ⁿ BuLi is added to a THF solution of cyclopentadienyl (Cp) manganese tricarbonyl compound (1), then 1,2-dibromotetrachloroethane is added and reacted, and the resulting reaction solution is subjected to a conventional method. To obtain ブ ロ モ⁵ -bromocyclopentadienyl manganese (I) tricarbonyl compound (2).

Next, lithium tetramethylpiperidide and dimethylformamide (DMF) are added dropwise to a THF solution of the compound (2) obtained above to make a reaction, and the resulting reaction solution is purified by a conventional method (±) -((Eta) < ⁵ >-1-bromo- 2-formyl cyclopentadienyl) manganese (I) tricarbonyl compound (3) can be obtained.

Then, methyltriphenylphosphonium iodide is added to a THF solution of the compound (3) obtained above to make a reaction, and the resulting reaction solution is purified by a conventional method to obtain (±)-(η ⁵ -1-). Bromo-2-vinylcyclopentadienyl) manganese (I) tricarbonyl compound (4) can be obtained.

Then, to a benzene solution of the compound (4) obtained above, the following formula:
(Wherein, R 'represents a hydrogen atom, optionally substituted by C ₁ optionally -C ₄ alkyl or C ₁ -C ₄ alkyl optionally substituted in the aryl group with a group with an aryl group , R ′ ′ is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group)
Was added, subjected to light irradiation reaction using a mercury lamp as a light source, the resulting reaction solution was purified by a conventional method (±) - (eta ^{5-1-bromo-2-vinyl-cyclopentadienyl)} (allyl phosphine ) Manganese (I) dicarbonyl compounds (5) can be obtained.

Next, a solution of the compound (5) obtained above and Grubbs-II catalyst (Grubbs-II) in dichloromethane (CH ₂ Cl ₂ ) is stirred and subjected to a metathesis reaction, and the obtained reaction solution is subjected to a conventional method purified to (±) - can be obtained [(eta ^5-1-bromo-2- (3-phosphino-1-propenyl) cyclopentadienyl -P)] manganese (I) dicarbonyl compound (6) .

Incidentally, the above obtained (±) compound which is the body (6) is optically resolved by chiral column chromatography, (+) - [(eta ^5-1-bromo-2- (3-diphenylphosphino - 2-methyl-propenyl) cyclopentadienyl -P)] manganese (I) dicarbonyl compound (6) and ^{(-) - [(η 5} -1- bromo-2- (3-diphenylphosphino-2-methyl-propenyl ) Cyclopentadienyl-P)] manganese (I) dicarbonyl compounds (6) can be obtained.

Further, ^t BuLi and then R ₂ PCl (R = 3,5-xylyl group or phenyl group) are added dropwise to the THF solution of the compound (6) which is (+), (-) or (±) form and then reacted is allowed, the resulting reaction solution was purified by a conventional method, each of which corresponds to the starting material (+), (-) or (±) - [(eta ^{5-1-phosphino-2-} (3-phosphino-2- Propenyl) cyclopentadienyl-P)] manganese (I) dicarbonyl (7) can be obtained.

Obtained in the above (+) - [(eta ^{5-1-phosphino-2-} (3-phosphino-2-propenyl) cyclopentadienyl -P]] manganese (I) dicarbonyl (7), or (- )-[(Η ⁵ -Phosphino-2- (3-phosphino-2-propenyl) cyclopentadienyl-P)] manganese (I) dicarbonyl (7) is a catalytic amount of a transition metal catalyst, For example, in the presence of rhodium and boronic acid compounds, 1,4-adducts are produced with high yield and extremely high optical purity not only to enone compounds, especially to cyclic enone compounds but also to aliphatic enone compounds. It is also a feature of the present invention to obtain.

The substituent R in the compound described in the above-mentioned synthetic scheme 1 is an aryl group which may be optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group, and the substituent R ′ is hydrogen atom, optionally substituted with an aryl group optionally substituted with even better C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyl group is also substituted aryl group, the substituents R "is And C ₁ -C ₄ alkyl groups or aryl groups optionally substituted with C ₁ -C ₄ alkyl groups.

  Preferably, said R is an isopropyl group, a phenyl group or a 3,5-xylyl group, said R 'is a hydrogen atom, a methyl group, an isopropyl group, a phenyl group or a benzyl group, and said R "is an isopropyl group, a phenyl group A group or 3,5-xylyl group.

  More preferably, the R is a phenyl group or a 3,5-xylyl group, the R 'is a methyl group or an isopropyl group, and the R "is a phenyl group or a 3,5-xylyl group.

The asymmetric ligand for transition metal complex formation of the present invention can be used for transition metal catalyzed asymmetric reaction in the presence of a transition metal salt or a transition metal complex precursor. The asymmetric ligand for transition metal complex formation of the present invention functions as a catalyst composition by being combined with a transition metal salt or a transition metal complex precursor.
Transition metal catalyzed asymmetric reactions include transition metal catalyzed asymmetric allylic amination, asymmetric allylic thioetherification, asymmetric allylic alkynylation or asymmetric Suzuki-Miyaura cross coupling reaction; organoboron Asymmetric 1,4-addition reaction of acid to enone compound or asymmetric 1,2-addition reaction to imine compound; Asymmetric 1,4-addition reaction of organic zinc compound to enone compound or imine compound Or an asymmetric 1,4-addition reaction of an organic titanium compound to an enone compound or an asymmetric 1,2-addition reaction to an imine compound.

  The asymmetric ligand for transition metal complex formation of the present invention functions as a catalyst composition by coordinating to a transition metal in the presence of a transition metal salt or a transition metal complex precursor. The asymmetric ligand for transition metal complex formation and the transition metal salt or transition metal complex precursor can be charged simultaneously or separately in the target reaction system to function as a catalyst composition. Although the compositional ratio of the transition metal complex-forming asymmetric ligand to the transition metal salt or transition metal complex precursor varies depending on the intended reaction, it is relative to 1 mole of transition metal complex-forming asymmetric ligand. 0.8-1.2 mol is preferable in conversion of a transition metal, and 1 mol is more preferable.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following description contents.
In the examples, unless otherwise specified, reagents available on the market were used, and the following various solvents, carriers for chromatography, columns for HPLC, and various analyzers were used:
Tetrahydrofuran (THF): manufactured by Wako, (super dehydrated);
Hexane: manufactured by Kishida Chemical Co., Ltd. (first grade);
Ethyl acetate (EtOAc): manufactured by Kishida Chemical Co., Ltd. (primary);
Benzene: manufactured by Kishida Chemical Co., Ltd. (first grade);
Dichloromethane: manufactured by Wako, (super dehydrated);
Dioxane: manufactured by Wako, (special grade);
Isopropanol: manufactured by Wako, (for high performance liquid chromatograph);

Silica gel for regular column chromatography (SiO ₂ ): manufactured by Kanto Chemical Co., Ltd., (spherical silica gel), 100-210 μm (particle diameter)
Chiral column for HPLC: Daicel, Chiralcel OD (φ 20 mm) column;
¹ H-NMR: manufactured by Nippon Denshi Datum Co., Ltd. (JEOL), ECX-400 (400 MHz),
¹³ C-NMR: manufactured by Nippon Denshi Datum Co., Ltd. (JEOL), ECX-400 (100 MHz),
³¹ P-NMR: manufactured by Nippon Denshi Datum Co., Ltd. (JEOL), ECX-400 (162 MHz),
IR: manufactured by JASCO, (FT / IR-4100);
HPLC: manufactured by JASCO, detector; no differential refractive index detector;
UV detector UV-2075 Plus;
Delivery unit; PU-2089 Plus:
HRMS: manufactured by JEOL, MStation JMS-700 model number;
Polarimeter: manufactured by JASCO P-2200 model number;
Elemental Analyzer: Perkin Elmer, Series II CHNS / O Analyzer

  In nuclear magnetic resonance (NMR) spectra, chemical shifts δ are expressed in parts per million (ppm), and the abbreviations respectively mean the following terms: s: singlet; d: doublet; dd: double doublet; t: triplet; m: multiplet.

Reference Example 1
The following synthesis scheme 2 shows synthesis steps of the compound 6 ′, the compounds 1a ′ to 1f ′, the compounds 2a ′ to 2f ′, and the compounds 3a ′ to 3h ′ used in comparative examples in the present application. This synthesis method is in accordance with the method disclosed in the above-mentioned Non-patent Document 1.
Wherein R represents an isopropyl group, a phenyl group or a 3,5-xylyl group, R ′ represents a hydrogen atom, a methyl group or a benzyl group, and R ′ ′ represents an isopropyl group, a phenyl group or 3 Means a -5- xylyl group)

  The synthesis method and physical data of the compound 6 ', the compounds 1a' to 1f ', the compounds 2a' to 2f 'and the compounds 3a' to 3h 'described above are specifically shown in the following Preparation Examples.

Reference Production Example 1
Preparation of (R)-or (S)-(η ⁶ -1-bromo-2-vinylbenzene) chromium tricarbonyl (6 ')
6 '
_{MePPh 3 · I (1.43g, 3.54} mmol, 1.3 eq) in THF suspension (95 mL) ^{of, t BuOK (458 mg, 4.08} mmol, 1.5 eq) was added and stirred at room temperature for 15 minutes. A THF (5 mL) solution of o-bromobenzaldehyde chromium complex optically active about plane asymmetry, which is a known compound of synthesis, was added to the above suspension and the mixture was further stirred for 1 hour. The mixture solution was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Subsequently, the organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column (hexane / EtOAc = 5/1) to give the title compound 6 'as orange crystals (435 mg, 1.71 mmol, 63%).
The ¹ H-NMR and ¹³ C-NMR spectra of the compound 6 'are shown in FIGS. 1-1 and 1-2, respectively.

¹ H NMR (C ₆ D ₆ ): δ 4.15-4.18 (m, 1H), 4.23-4.26 (m, 1H), 4.79-4.85 (m, 2H), 4.91 (d, J = 10.9 Hz, 1H) , 5.15 (d, J = 17.4 Hz, 1 H), 6.46 (dd, J = 17.4 and 10.9 Hz, 1 H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 89.5, 89.6, 91.9, 94.7, 99.5, 104.2, 117.8, 133.0, 232.2.
EI-HRMS theory _{(C 11 H 7 BrCrO 3)} :. 317.8984 Found: 317.8981.
[α] _D ²³ -610 (c 0.50, EtOAc, (R) -enantiomer).

Reference Production Example 2
preparation of (eta ^{6-1-bromo-2-vinylbenzene)} (allylic phosphine) chromium (0) dicarbonyl (1a '-f')
Wherein R represents an isopropyl group, a phenyl group or a 3,5-xylyl group, and R ′ represents a hydrogen atom, a methyl group or a benzyl group.
(R)-or (S)-(η ⁶ -1-bromo-2-vinylbenzene) chromium complex 6 '(590 mg, 1.85 mmol) and (2-substituted allyl) phosphine (1.5 eq) in a nitrogen atmosphere, It was dissolved in benzene (15 mL). The solution was irradiated with UV light using a mercury lamp and stirred at room temperature for 7 hours. The resulting red solution was filtered and concentrated under reduced pressure. The crude product was purified by silica gel column (hexane / EtOAc = 10/1) to give the title compound 1 as red crystals or oil. The reaction conditions are not optimized. The yields of 1a'-f 'are listed in scheme 1. Physical property data of the chromium complex 1a'-f 'are shown in the following Reference Production Examples 2-a to 2-f.

Reference Production Example 2-a
(S) - (+) - (η 6 -1- bromo-2-vinylbenzene) [(2-methylallyl) diphenylphosphine] chromium (0) in Preparation Example 2 of dicarbonyl (1a ') (2-substituted The following compound 1a ′ was obtained in a yield of 63% in the same manner as in allyl) phosphine except that 2-methylallyldiphenylphosphine was used.
1a '

¹ H NMR (C ₆ D ₆ ): δ 1.25 (s, 3 H), 3.05 (d, J = 8.4 Hz, 2 H), 3.7-3.83 (m, 1 H), 3.98-4.03 (m, 1 H), 4.61 -4.64 (m, 1H), 4.65-4.66 (m, 1H), 4.71-4.74 (m, 1H), 4.77-4.79 (m, 1H), 4.92 (d, J = 10.9 Hz, 1H), 5.16 (d , J = 17.2 Hz, 1 H), 6.84, (dd, J = 17.2 and 10.9 Hz, 1 H), 7.00-7.08 (m, 6 H), 7. 45-7. 55 (m, 4 H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 24.6 (d, J _PC = 1.5 Hz), 43.3 (d, J _PC = 19.1 Hz), 86.3 (s), 88.5 (s), 91.2 (9 s), 91.5 (s), 96.6 (s), 98.2 (s), 115.2 (s), 116.8 (d, J PC = 8.3 Hz), 128.19 (d, J PC = 8.2 Hz), 128.20 (d, J _{PC = 8.5 Hz), 129.2 (} d, J PC = 2.1 Hz), 129.4 (d, J PC = 2.1 Hz), 132.6 (d, J PC = 10.0 Hz), 132.8 (d, J PC = 10.3 Hz), 135.1 (s), 139.2 (d , J PC = 5.9 Hz), 140.1 (d, J PC = 29.1 Hz), 140.3 (d, J PC = 29.2 Hz), 239.3 (d, J PC = 19.4 Hz), 239.5 (d, J _PC = 20.0 Hz).
³¹ P {1 H} NMR (C ₆ D ₆ ): δ 81.2 (s).
IR (KBr) 1896, 1846, 1091 cm ^-1 .
Elementary analysis: Calculated _{(C 26 H 24 BrCrO 2 P} ):. C, 58.77; H, 4.55 Found: C, 58.85; H, 4.65 .
EI-HRMS: theory _{(C 26 H 24 BrCrO 2 P} ):. 530.0102 Found: 530.0112.
^{_{[α] D 25 +186 (c}} 0.46, CHCl 3).

Reference Production Example 2-b
(S) - (+) - (η 6 -1- bromo-2-vinylbenzene) [diisopropyl (2-methylallyl) phosphine] chromium (0) in Preparation Example 2 of dicarbonyl (1b ') (2-substituted The following compound 1b ′ was obtained in a yield of 64% in exactly the same manner as using 2-methylallyldidiisopropylphosphine as allyl) phosphine.
1b '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 1b ′ are shown in FIGS.

¹ H NMR (C ₆ D ₆ ): δ 0.92-1.05 (m, 12 H), 1.68 (s, 3 H), 1.77-1.89 (m, 2 H), 2.42 (d, J = 7.1 Hz, 2 H), 4.24 -4.27 (m, 1H), 4.36-4.40 (m, 1H), 4.80 (br, 2H), 4.87 (d, J = 10.9 Hz, 1H), 4.95-5.01 (m, 2H), 5.30 (d, J = 17.2 Hz, 1 H), 6.94 (dd, J = 17.2 and 10.9 Hz, 1 H).
^{13 C {1 H} NMR (} C 6 D 6): δ18.7 (d, J PC = 1.8 Hz), 18.8 (d, J PC = 1.8 Hz), 19.1 (s), 19.2 (s), 25.6 ( s), 28.7 (d, J PC = 14.9 Hz), 28.8 (d, J PC = 14.9 Hz), 36.2 (d, J PC = 12.8 Hz), 83.9 (s), 85.3 (s), 88.9 (s) , 89.2 (s), 95.0 ( s), 98.3 (s), 114.7 (s), 115.6 (d, J PC = 6.2 Hz), 135.7 (s), 141.3 (d, J PC = 8.0 Hz), 240.2 ( d, J _PC = 19.2 Hz), 240.3 (d, J _PC = 19.5 Hz).
^{31 P {1 H} NMR (} C 6 D 6): δ85.6 (s).
EI-HRMS: theory _{(C 20 H 28 BrCrO 2 P} ):. 462.0415 Found: 462.0413.
[[alpha]] _D ²⁵ + 451 (c 0.50, EtOAc).

Reference Production Example 2-c
(S) - (+) - preparation of (eta ^{6-1-bromo-2-vinylbenzene)} [bis (3,5-dimethylphenyl) (2-methylallyl) phosphine] chromium (0) dicarbonyl (1c ') The following compound 1c ′ was obtained in a yield of 68% in the same manner as in Production Example 2 except that 2-methylallyldixylylphosphine was used as (2-substituted allyl) phosphine.
1c '

The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 1c ′ are shown in FIGS. 3-1 to 3-3.

¹ H NMR (C ₆ D ₆ ): δ 1.38 (s, 3 H), 2. 10 (d, J = 2.5 Hz, 12 H), 3. 18 (d, J = 8.5 Hz, 2 H), 3.99-4.03 (m, 1 H) ), 4.12-4.16 (m, 1H), 4.65-4.67 (m, 1H), 4.74-4.78 (m, 2H), 4.87-4.89 (m, 1H), 4.94 (d, J = 10.7, 1H), 5.18 (d, J = 17.2 Hz, 1 H), 6.71 (s, 2 H), 6. 93 (dd, J = 17.2 and 10.8 Hz, 1 H), 7. 39 (t, J = 10.8 Hz, 4 H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 21.4 (s), 21.4 (s), 24.7 (s), 43.5 (d, J _PC = 19.0 Hz), 85.8 (s), 88.5 (s ), 91.1 (s), 91.7 (s), 96.7 (s), 98.3 (s), 115.1 (s), 116.7 (d, J PC = 8.2 Hz), 128.4, 130.6 (d, J PC = 10.0 Hz) _{, 130.6 (d, J PC =} 10.3 Hz), 131.2 (s), 131.2 (s), 135.4 (s), 137.6 (d, J PC = 8.9 Hz), 139.5 (d, J PC = 5.4 Hz), 140.1 (d, J _PC = 29.2 Hz), 140.2 (d, J _PC = 29.3 Hz), 239.7 (d, J _PC = 20.5 Hz), 239.9 (d, J _PC = 20.7 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 79.6 (s).
EI-HRMS: theory _{(C 30 H 32 BrCrO 2 P} ):. 586.0728 Found: 586.0727.
[[alpha]] _D ²⁴ + 462 (c 0.50, EtOAc).

Reference Production Example 2-d
Preparation of (R)-(-)-(η ⁶ -1-bromo-2-vinylbenzene) [diphenyl (2-phenylallyl) phosphine] chromium (0) dicarbonyl (1 d ′) The following compound 1d ′ was obtained in a yield of 62% in the same manner as that described above except that 2-phenylallyldiphenyl phosphine was used as a substituted allyl) phosphine.
1d '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 1d ′ are shown in FIGS.

¹ H NMR (C ₆ D ₆ ): δ 3.49 (d, J = 8.3 Hz, 2 H), 3.73 (dd, J = 9.1 and 5.8 Hz, 1 H), 3.95 (dd, J = 10.9 and 5.2 Hz, 1 H ), 4.48 (d, J = 6.2 Hz, 1 H), 4. 64 (d, J = 6.2 Hz, 1 H), 4. 78 (d, J = 3.6 Hz, 1 H), 4.92 (d, J = 10.8 Hz, 1 H), 5.12-5.18 (m, 2H), 6.79 (dd, J = 17.2 Hz and 10.8 Hz, 1H), 6.94-6.98 (m, 9H), 7.08-7.10 (m, 2H), 7.43-7.50 (m, 4H) .
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 40.2 (d, J _PC = 17.1 Hz), 86.4 (s), 88.9 (s), 91.5 (s), 91.7 (s), 96.4 (s) ), 98.0 (s), 115.2 (s), 118.6 (d, J PC = 7.8 Hz), 126.8 (s), 127.1 (s), 128.0 (s), 128.2 (s), 128.6 (s) 129.2 (s ), 129.3 (s) 132.7 ( d, J PC = 10.6 Hz), 132.8 (d, J PC = 10.9 Hz), 135.0 (s) 139.5 (d, J PC = 30.6 Hz), 139.6 (d, J PC = 30.3 Hz), 141.9 (d, J PC = 4.9 Hz), 142.5 (d, J PC = 1.5 Hz), 239.4 (d, J PC = 21.0 Hz), 239.7 (d, J PC = 22.0 Hz).
^{31 P {1 H} NMR (} C 6 D 6): δ82.8 (s).
EI-HRMS: theory _{(C 31 H 26 BrCrO 2 P} ):. 592.0259 Found: 592.0248.
^{_{[α] D 22 -427 (c}} 1.00, benzene).

Reference Production Example 2-e
(S) - (+) - as (eta ^{6-1-bromo-2-vinylbenzene)} (allyldiphenylphosphine) chromium (0) (2-substituted aryl) in Preparation Example 2 of dicarbonyl (1e ') phosphine The following compound 1e 'was obtained in a yield of 66% in exactly the same manner as in Example 1 except that allyl diphenyl phosphine was used.
1e '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 1e ′ are shown in FIGS. 5-1 to 5-3.

¹ H NMR (C ₆ D ₆ ): δ 3.02-3.06 (m, 2 H), 3.82-3.86 (m, 1 H), 3.98-4.03 (m, 1 H), 4.65-4.68 (m, 1 H), 4.71- 4.77 (m, 2H), 4.83-4.87 (m, 1H), 4.92 (d, J PC = 10.8 Hz, 1H), 5.16 (d, J PC = 17.2 Hz, 1H), 5.60-5.72 (m, 1H) _{, 6.88 (dd, J PC =} 17.2 and 10.8 Hz, 1H), 6.99-7.09 ( m, 6H), 7.38-7.48 (m, 4H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 40.0 (d, J = 22.8 Hz), 86.1 (s), 88.2 (s), 90.8 (s), 91.2 (s), 96.9 (s) , 98.1 (s), 115.2 (s), 119.3 (d, J = 10.3 Hz), 128.2, 128.3, 128.3, 129.2 (d, J _PC = 1.6 Hz), 129.3 (d, J _PC = 1.5 Hz), 131.0 _{(d, J PC = 4.6 Hz} ), 132.5 (d, J PC = 10.0 Hz), 132.7 (d, J PC = 10.0 Hz), 135.2 (s), 139.3 (d, J PC = 29.7 Hz), 139.5 ( d, J _PC = 29.7 Hz), 239.0 (d, J _PC = 20.3 Hz), 239.2 (d, J _PC = 20.7 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 80.0 (s).
EI-HRMS: theory _{(C 25 H 22 BrCrO 2 P} ):. 515.9946 Found: 515.9940.
[[alpha]] _D ²⁶ + 372 (c 0.50, EtOAc).

Reference Production Example 2-f
Preparation of (R)-(-)-(η ⁶ -1-bromo-2-vinylbenzene) [(2-benzylallyl) diphenylphosphine] chromium (0) dicarbonyl (1f ′) In Preparation Example 2 (2- The following compound 1f ′ was obtained in a yield of 65% in the same manner as that described above except that 2-benzylallyldiphenyldiphenylphosphine was used as a substituted allyl) phosphine.
1f '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 1f ′ are shown in FIGS. 6-1 to 6-3.

¹ H NMR (C ₆ D ₆ ): δ 2.90 (s, 2H), 2.99-3.08 (m, 2H), 3.79-3.83 (m, 1H), 3.99-4.03 (m, 1H), 4.64 (d, 5d) J = 6.4 Hz, 1 H), 4.73-4. 83 (m, 3 H), 4. 93 (d, J = 10.8 Hz, 1 H), 5. 17 (d, J = 17.2 Hz, 1 H), 6. 85 (dd, J = 17.2 Hz and 10.8 Hz, 1 H), 6.97-7.14 (m, 11 H), 7.45-7.54 (m, 4 H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 40.7 (d, J _PC = 18.4 Hz), 44.3 (s), 86.5 (s), 88.6 (s), 91.4 (s), 91.6 (s) ), 96.6 (s), 98.4 (s), 115.3 (s), 118.2 (d, J PC = 7.8 Hz), 126.5 (s), 128.2, 128.3, 128.5 (s), 128.6 (s), 129.3 (s ), 129.4 (s), 129.5 (s), 132.6 (d, J PC = 9.8 Hz), 132.8 (d, J PC = 10.1 Hz) 135.0 (s), 139.5 (s), 140.2 (d, J PC = 29.3 Hz), 140.4 (d, J PC = 29.5 Hz), 142.1 (d, J PC = 4.9 Hz), 239.4 (d, J PC = 20.4 Hz), 239.7 (d, J PC = 21.0 Hz).
^{31 P {1 H} NMR (} C 6 D 6): δ82.4 (s).
EI-HRMS: theory _{(C 32 H 28 BrCrO 2 P} ):. 606.0415 Found: 606.0400.
^{_{[α] D 25 -164 (c}} 0.96, benzene).

Reference Production Example 3
Preparation of [η ⁶ -1-Bromo-2- (3-di-R-phosphino-2-R'-propenyl) benzene-P] chromium (0) Dicarbonyl (2a'-2f ')
Wherein R represents an isopropyl group, a phenyl group or a 3,5-xylyl group, and R ′ represents a hydrogen atom, a methyl group or a benzyl group.
(R)-or (S)-(η ⁶ -1-bromo-2-vinylbenzene) (arylic phosphine) chromium complex 1 (1.39 mmol) and Grubbs-II (5 mol%) in dichloromethane under nitrogen atmosphere It was dissolved in 10 mL). The solution was stirred at 50 ° C. for 18 hours. The yellow solution was filtered and concentrated under reduced pressure. The crude product was purified by silica gel column (hexane / EtOAc = 10/1) to give the title compound as yellow crystals or oil. The reaction conditions are not optimized. The yields of 2a'-f 'are listed in Table 1 below. Physical property data of the chromium complex 2a'-f 'are shown in the following Production Examples 3-a to 3-f.

Reference Production Example 3-a
(S) - (-) - [eta ^6-1-bromo-2- (3-diphenylphosphino-2-methyl-propenyl) benzene -P] Chromium - (0) prepared in Reference Preparation Example dicarbonyl (2a ') The following compound 2a ′ was obtained in a yield of 91% in the same manner as in 3, except that 2-methylallyldiphenylphosphine 1a ′ was used as the arylic phosphine.
2a '

¹ H NMR (C ₆ D ₆ ): δ 1.43 (d, J = 0.9 Hz, 3 H), 2.56 (dd, J = 14.7 and 7.8 Hz, 1 H), 2.81 (dd, J = 14.7 and 10.9 Hz, 1 H ), 3.96-3.99 (m, 1H), 4.14-4.17 (m, 1H), 4.41-4.44 (m, 1H), 5.19-5.21 (m, 1H), 6.02 (br, 1H), 6.95-7.12 (m , 6H), 7.41-7.49 (m, 4H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 27.2 (d, JPC = 4.6 Hz), 35.4 (d, JPC = 15.4 Hz), 79.9 (s), 86.5 (s), 91.1 (d, JPC = 1.7 Hz), 91.92 (s), 91.94 (d, JPC = 1.3 Hz), 100.9 (d, JPC = 3.0 Hz), 122.0 (d, JPC = 11.0 Hz), 128.2 (d, JPC = 9.0 Hz) , 128.4 (d, JPC = 9.0 Hz), 129.28 (d, JPC = 2.4 Hz), 129. 32 (d, JPC = 2.0 Hz), 132.0 (d, JPC = 10.4 Hz), 132.3 (d, JPC = 10.7) Hz), 138.0 (s), 138.8 (d, JPC = 35.6 Hz), 140.7 (d, JPC = 35.0 Hz), 237.0 (d, JPC = 19.0 Hz), 238.3 (d, JPC = 18.3 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 99.6 (s). IR (KBr) 1899, 1846 cm ⁻¹ .
Elementary analysis: Calculated _{(C 24 H 20 BrCrO 2 P} ):. C, 57.27; H, 4.01 Found: C, 57.04; H, 4.02 .
EI-HRMS: theory _{(C 24 H 20 BrCrO 2 P} ):. 501.9789 Found: 501.9785.
[[alpha]] _D ²⁵ -66.3 (c 1.20, EtOAc,> 99% ee).

Reference Production Example 3-b
Preparation of (S)-(+)-[η ⁶ -1-bromo-2- (3-diisopropylphosphino-2-methylpropenyl) benzene-P] chromium (0) dicarbonyl (2b ′) Reference Preparation Example 3 The following compound 2b ′ was obtained in a yield of 89% in exactly the same manner as in Example 1 except that 2-methylallyldiisopropylphosphine was used as the arylic phosphine.
2b '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 2b ′ are shown in FIGS. 7-1 to 7-3.

¹ H NMR (C ₆ D ₆ ): δ 0.78-1.04 (m, 12 H), 1.51-1. 58 (m, 1 H), 1. 64 (t, J = 1.4 Hz, 3 H), 1.71-1. 95 (m, 3 H) , 3.91-3.94 (m, 1 H), 4.14-4.23 (m, 2 H), 5.03 (d, J = 6.0 Hz, 1 H), 6.08-6. 10 (m, 1 H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 16.9 (d, J _PC = 2.3 Hz), 17.2 (s), 17.6 (d, J _PC = 3.6 Hz), 18.4 (d, J _PC = 3.1 Hz), 26.2 (d, J PC = 8.2 Hz), 27.1 (d, J PC = 4.4 Hz), 27.7 (d, J PC = 21.8 Hz), 30.2 (d, J PC = 18.4 Hz), 80.2 ( s), 87.9 (s), 88.4 (s), 89.5 (d, J PC = 1.8 Hz), 96.3 (s), 97.5 (d, J PC = 2.0 Hz), 122.4 (d, J PC = 8.5 Hz) , 137.3 (s), 239.2 (d, J _PC = 17.7 Hz), 241.1 (d, J _PC = 17.6 Hz).
^{31 P {1 H} NMR (} C 6 D 6): δ114.2 (s).
EI-HRMS: theory _{(C 18 H 24 BrCrO 2 P} ):. 434.0102 Found: 434.0103.
[[alpha]] _D ²³ + 214 (c 0.50, EtOAc).

Reference Production Example 3-c
(S)-(-)-[η ⁶ -1-bromo-2- (3-bis (3,5-dimethylphenyl) phosphino-2-methylpropenyl) benzene-P] chromium (0) dicarbonyl (2c ′ Preparation of) The following compound 2c 'was obtained in a yield of 93% in the same manner as in Reference Production Example 3 except that 2-methylallyldixylylphosphine was used as the arylic phosphine.
2c '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 2c ′ are shown in FIGS. 8-1 to 8-3.

¹ H NMR (C ₆ D ₆ ): δ 1.49 (s, 3 H), 2.09 (s, 12 H), 2.69-2.75 (m, 1 H), 2.99 (dd, J = 14.4 and 11.7, 1 H), 4.02- 4.06 (m, 1H), 4.11-4.15 (m, 1H), 4.47 (t, J = 5.8 Hz, 1 H), 5.25 (d, J = 6.2 Hz, 1 H), 6.09 (t, J = 1.3 Hz, 1 H) ), 6.72 (d, J = 12.2 Hz, 2 H), 7. 29 (d, J = 10.1 Hz, 2 H), 7. 36 (d, J = 10.4 Hz, 2 H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 21.4 (s), 21.4 (s), 27.4 (d, J _PC = 4.4 Hz), 35.6 (d, J _PC = 15.4 Hz), 79.4 (7 s), 86.0 (s), 91.5 (s), 91.7 (s), 91.8 (s), 101.0 (d, J PC = 2.8 Hz), 122.1 (d, J PC = 11.1 Hz), 129.5 (d, J _{PC = 10.0 Hz), 130.7 (} d, J PC = 10.7 Hz), 131.2 (d, J PC = 1.3 Hz), 131.4 (d, J PC = 1.5 Hz), 137.5 (d, J = 9.5 Hz), 137.8 (d, J _PC = 9.2 Hz), 137.9 (d, J _PC = 34.6 Hz), 138.2 (s), 140.8 (d, J _PC = 35.9 Hz), 237.6 (d, J _PC = 19.5 Hz), 238.4 ( d, J _PC = 17.7 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 99.1 (s).
EI-HRMS: theory _{(C 28 H 28 BrCrO 2 P} ):. 558.0415 Found: 558.0408.
[[alpha]] _D ²⁴ -64.1 (c 0.50, EtOAc).

Reference Production Example 3-d
(R) - (-) - [η 6 -1- bromo-2- (3-diphenylphosphino-2-phenyl-propenyl) benzene -P] chromium (0) prepared in Reference Preparation Example 3 of dicarbonyl (2d ') The following compound 2d ′ was obtained in a yield of 80% in exactly the same manner as in Example 1 except that 2-phenylallyldiphenylphosphine was used as allyl phosphine.
2d '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 2d ′ are shown in FIGS. 9-1 to 9-3.

¹ H NMR (C ₆ D ₆ ): δ 2.89-2.95 (m, 1 H), 3.50 (dd, J = 14.9, 11.8 Hz, 1 H), 4.08 (td, J = 6.3, 1.1 Hz 1 H), 4.19 (4 t, J = 5.9 Hz, 1 H) 4. 38 (t, J = 6.0 Hz, 1 H), 5.21 (d, J = 6.0 Hz, 1 H), 6. 60 (t, J = 2.5 Hz, 1 H), 6.91-7. 13 (m , 11 H), 7.46-7.51 (m, 4 H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 35.4 (d, J _PC = 14.6 Hz), 80.1 (s), 86.4 (s), 90.9 (s), 91.2 (s), 93.3 (s) _{), 99.2 (d, J PC} = 2.6 Hz), 125.3 (d, J PC = 10.8 Hz), 126.8 (s), 127.9 (s), 128.3 (s), 128.3 (s), 128.5 (d, J PC = 9.2 Hz), 128.7 (s ), 129.4 (s), 129.5 (s) 132.1 (d, J PC = 10.3 Hz), 132.4 (d, J PC = 10.6 Hz), 138.3 (d, J PC = 34.9 Hz _{), 140.4 (d, J PC} = 36.4 Hz), 140.9 (s), 143.9 (d, J PC = 4.8 Hz), 236.9 (d, J PC = 19.2 Hz), 238.4 (d, J PC = 17.7 Hz) .
^{31 P {1 H} NMR (} C 6 D 6): δ103.4 (s).
EI-HRMS: theory _{(C 29 H 22 BrCrO 2 P} ):. 563.9946 Found: 563.9954.
^{_{[α] D 21 -2.38 (c}} 2.73, benzene).

Reference Production Example 3-e
(S) - (+) - a [eta ^6-1-bromo-2- (3-diphenylphosphino-propenyl) benzene -P] chromium (0) allyl phosphine in the production Reference Preparation Example 3 of dicarbonyl (2e ') The following compound 2e ′ was obtained in a yield of 55% in the same manner as in Example 1 except that allyl diphenyl phosphine was used.
2e '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 2e ′ are shown in FIGS. 10-1 to 10-3.

¹ H NMR (C ₆ D ₆ ): δ 2.35-2.42 (m, 1 H), 2.76-2.85 (m, 1 H), 3.95 (td, J = 6.2 and 1.3 Hz, 1 H), 4.16 (tt, J = 6.1 and 1.1 Hz, 1 H), 4.34 (t, J = 6.0 Hz, 1 H), 5.16 (d, J = 6.2 Hz, 1 H), 5.50-5.59 (m, 1 H), 6.24-6.28 (m, 1 H), 6.97-7.13 (m, 6H), 7.43-7.49 (m, 4H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 30.0 (d, J _PC = 15.6 Hz), 80.4 (s), 87.3 (s), 90.4 (s), 91.2 (s), 92.6 (s) _{), 97.6 (d, J PC} = 3.3 Hz), 128.2 (s), 128.3 (s), 128.4 (s), 128.5 (s), 128.9 (s), 129.3 (d, J PC = 2.1 Hz), 132.1 _{(d, J PC = 10.2 Hz} ), 132.2 (d, J PC = 10.2 Hz), 138.9 (d, J PC = 35.7 Hz), 140.7 (d, J PC = 35.6 Hz), 236.9 (d, J PC = 18.9 Hz), 238.7 (d, J _PC = 18.2 Hz).
^{31 P {1 H} NMR (} C 6 D 6): δ100.0 (s).
EI-HRMS: theory _{(C 24 H 23 BrCrO 2 P} ):. 505.0024 Found: 505.0022.
[α] _D ²⁶ +29.9 (c 0.50, EtOAc).

Reference Production Example 3-f
Preparation of (R)-(+)-[η ⁶ -1-Bromo-2- (2-benzyl-3-diphenylphosphinopropenyl) benzene-P] chromium (0) Dicarbonyl (2f ′) Reference Preparation Example 3 The following compound 2f ′ was obtained in a yield of 65% in exactly the same manner as in Example 1 except that 2-benzylallyldiphenyl phosphine was used as allyl phosphine.
2f '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 2f ′ are shown in FIGS. 11-1 to 11-3.

¹ H NMR (C ₆ D ₆ ): δ 2.63-2.69 (m, 1 H), 2.94-3.06 (m, 3 H), 3.94 (t, J = 5.6 Hz, 1 H), 4.14 (t, J = 5.9 Hz) , 1H), 4.40 (t, J = 6.0 Hz, 1 H), 5.21 (d, J = 6.0 Hz, 1 H), 6.06 (s, 1 H), 6.93-7.15 (m, 11 H), 7.38-7.46 (m, 4H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 34.3 (d, J _PC = 15.2 Hz), 47.5 (d, J _PC = 2.6 Hz), 79.9 (s), 86.5 (s), 91.2 (9 s), 91.9 (s), 91.9 (s), 100.6 (s), 123.7 (d, J _PC = 10.7 Hz), 126.9 (s), 128.1, 128.4, 128.6, 128.9 (s), 129.3 (s), 129.3 (s) 129.6 (s), 132.0 (d, J _PC = 10.3 Hz), 132.4 (d, J _PC = 10.3 Hz), 138.3 (s) 138.6 (d, J _PC = 35.9 Hz), 140.5 (d, J _PC = 35.4 Hz), 141.0 (s), 237.0 (d, J _PC = 18.9), 238.1 (d, J _PC = 18.0 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 100.2 (s).
EI-HRMS: theory _{(C 30 H 24 BrCrO 2 P} ):. 578.0102 Found: 578.0112.
[α] _D ²¹ + 65.5 (c 0.59, benzene).

Reference Production Example 4
Preparation of [η ⁶ -1- (di-R "-phosphino) -2- (3-di-R-phosphino-2-R'-propenyl) benzene-P] chromium (0) dicarbonyl (3 ')
Wherein R represents an isopropyl group, a phenyl group or a 3,5-xylyl group, R ′ represents a hydrogen atom, a methyl group or a benzyl group, and R ′ ′ represents an isopropyl group, a phenyl group or 3 Means a 5-xylyl group).
(R) - or (S) - [η ⁶ -1- bromo-2- (3-di -R- phosphino -2-R'- propenyl) benzene -P] chromium (0) dicarbonyl 2 '(0.40 mmol in THF solution) was added dropwise ^t BuLi (2.0 eq, 1.77 M pentane solution) under a nitrogen atmosphere, at -78 ° C.. After stirring for 30 minutes at −78 ° C., R ′ ′ ₂ PCl (1.3 eq) was added. The temperature was raised to room temperature over 2 hours, and the reaction was quenched with aqueous ammonium chloride. The reaction mixture was extracted with ethyl acetate The organic layer was dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column (hexane / benzene = 1/1) to give the title compound The reaction conditions are not optimized 3a'- The yields of f 'are listed in Table 1 below.
Physical property data of the chromium complex 3a'-f 'are shown in the following Production Examples 4-a to 4-h.

Reference Production Example 4-a
Preparation of (R)-(-)-[η ⁶ -1-Diphenylphosphino-2- (3-diphenylphosphino-2-methylpropenyl) benzene-P] chromium (0) Dicarbonyl (3a ') Reference Preparation Example 4 as (R)-or (S)-[η ⁶ -1-bromo-2- (3-di-R-phosphino-2-R′-propenyl) benzene-P] chromium (0) as a dicarbonyl, (R) - or (S) - [η ⁶ -1- bromo-2- (3-diphenylphosphino-2-methyl-propenyl) benzene -P] chromium (0) with a dicarbonyl 2a ', R _"2 PCl The following compound 3a ′ was obtained in a yield of 74% in exactly the same manner as in using chlorodiphenylphosphine as
3a '

¹ H NMR (C ₆ D ₆ ): δ 1.36 (s, 3 H), 3.03 (t, J = 13.4 Hz, 1 H), 3.60 (t, J = 7.0 Hz, 1 H), 4.13-4.19 (m, 2 H) ), 4.68 (d, J = 5.9 Hz, 1 H), 4. 90 (t, J = 5.8 Hz, 1 H), 5. 91 (s, 1 H), 7.03-7.19 (m, 12 H), 7.41 (t, J = 7.1 Hz) , 2H), 7.60-7.68 (m, 6H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 27.3 (d, JPC = 6.4 Hz), 36.7 (d, JPC = 14.0 Hz), 36.8 (d, JPC = 14.8 Hz), 80.6, 86.5 ( d, JPC = 3.7 Hz), 91.5 (d, JPC = 1.9 Hz), 92.1, 108.0 (d, JPC = 3.2 Hz), 108.3 (d, JPC = 3.3 Hz), 121.0 (d, JPC = 5.6 Hz), 121.0 (d, JPC = 5.6 Hz), 128.7, 128.8, 128.9, 129.4, 129.6, 131.2, 131.3, 133.2, 133.4, 135.6, 135.7, 135.9, 138.3, 139.3, 139.4, 130.0, 140.0, 140.0, 141.1, 141.4, 236.8 (d, JPC = 19.4 Hz), 239.1 (d, JPC = 20.9 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ-10.0 (s), 96.5 (s).
EI-HRMS: theory _{(C 36 H 30 CrO 2 P} 2):. 608.1126 Found, 608.1125.
[[alpha]] _D ²⁵ -433 (c 0.20, EtOAc).

Reference Production Example 4-b
Preparation of (R)-(-)-[η ⁶ -1-Diphenylphosphino-2- (3-diisopropylphosphino-2-methylpropenyl) benzene-P] chromium (0) Dicarbonyl (3b ') Reference Preparation Example 4 as (R)-or (S)-[η ⁶ -1-bromo-2- (3-di-R-phosphino-2-R′-propenyl) benzene-P] chromium (0) as a dicarbonyl, (R) - or (S) - [η ⁶ -1- bromo-2- (3-diisopropylphosphino-2-methyl-propenyl) benzene -P] chromium (0) with a dicarbonyl 2b ', R _"2 PCl The following compound 3b 'was obtained in a yield of 65% in exactly the same manner as in Example 1 except that chlorodiphenylphosphine was used.
3b '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 3b ′ are shown in FIGS. 12-1 to 12-3.

¹ H NMR (C ₆ D ₆ ): δ 0.90-1.06 (m, 6 H), 1.21-1.28 (m, 6 H), 1.54 (s, 3 H), 1.71-1.77 (m, 1 H), 1.86-2.04 (1.83) m, 2H), 2.15 (dd, J = 15.4 and 10.9, 1H), 3.96-4.00 (m, 1H), 4.18 (t, J = 6.1 Hz, 1H), 4.56-4.59 (m, 2H), 6.09 ( d, J = 1.5 Hz, 1 H), 7.03-7.11 (m, 4 H), 7.16-7.21 (m, 2 H), 7.42-7.46 (m, 2 H), 7.71-7. 75 (m, 2 H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 17.6 (s), 18.3 (s), 18.4 (s), 18.7 (s), 27.1 (d, J _PC = 4.4 Hz), 28.1 (dd , J _PC = 7.1 and 3.3 Hz), 28.5 (d, J _PC = 20.8 Hz), 29.7 (d, J _PC = 18.9 Hz), 80.9 (s), 87.2 (d, J _PC = 3.6 Hz), 87.6 (8 s), 91.1 (s), 96.0 (d, J PC = 13.1 Hz), 104.7 (d, J PC = 24.4 Hz), 121.5 (t, J PC = 8.4 Hz), 128.8 (d, J PC = 1.8 Hz ), 128.9 (s), 128.9 (s), 129.7 (s), 133.3 (d, J _PC = 19.8 Hz), 135.5 (d, J _PC = 14.4 Hz), 136.4 (d, J _PC = 21.3 Hz), _{138.1 (d, J PC = 2.6} Hz), 139.2 (d, J PC = 13.1 Hz), 239.9 (dd, J PC = 17.4 and 4.1 Hz), 241.1 (d, J PC = 18.7 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ-10.5 (s), 111.5 (s).
EI-HRMS: theory _{(C 30 H 34 CrO 2 P} 2):. 540.1439 Found: 540.1439.
[α] _D ²³ -365 (c 0.50, EtOAc).

Reference Production Example 4-c
(R)-(-)-[η ⁶ -1-diphenylphosphino-2- (3-bis (3,5-dimethylphenyl) phosphino-2-methylpropenyl) benzene-P] chromium (0) dicarbonyl ( Preparation of 3c ′) In Reference Preparation Example 4, (R)-or (S)-[η ⁶ -1-bromo-2- (3-di-R-phosphino-2-R′-propenyl) benzene-P] chromium (0) As dicarbonyl, (R)-or (S)-[η ⁶ -1-bromo-2- (3-di-3,5-xylphosphino-2-methylpropenyl) benzene-P] chromium (0) The following compound 3c 'was obtained in a yield of 55% in the same manner as in (2) except that dicarbonyl 2c' was used and chlorodiphenylphosphine was used as R " ₂ PCl.
3c '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 3c ′ are shown in FIGS. 13-1 to 13-3.

¹ H NMR (C ₆ D ₆ ): δ 1.45 (s, 3 H), 2. 10 (s, 6 H), 2. 19 (s, 6 H), 3. 17 (dd, J = 14.1 and 11.2 Hz, 1 H), 3.60-3.67 (m, 1H), 4.15-4.19 (m, 2H), 4.69-4.71 (m, 1H), 4.91 (dd, J = 5.9 and 5.9 Hz, 1H), 6.01 (s, 1H), 6.75 (d, J = 12.9 Hz, 2H), 7.03-7.09 (m, 4H), 7.16-7.21 (m, 2H), 7.41-7.50 (m, 4H), 7.56 (d, J = 10.0 Hz, 2H), 7.67-7. m, 2H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 21.5 (s), 21.5 (s), 27.4 (d, J _PC = 4.3 Hz), 36.8 (dd, J _PC = 14.4, 10.5 Hz), 80.4 (s), 86.6 (d , J PC = 3.8 Hz), 90.9 (d, J PC = 1.6 Hz), 92.2 (s), 92.3 (dd, J PC = 12.8 and 1.0 Hz), 108.0 (dd, J _PC = 25.6 and 3.1 Hz), 121.2 (dd, J PC = 11.0 and 6.2 Hz), 128.8 (d, J PC = 6.9 Hz), 128.8 (s), 129.0 (d, J PC = 6.7 Hz), 129.4 ( d, J _PC = 9.9 Hz), 129.5 (s), 130.7 (d, J _PC = 10.6 Hz), 131.1 (s), 131.3 (s), 133.4 (d, J _PC = 20.0 Hz), 135.5 (d, _{J PC = 20.5 Hz), 136.0} (d, J PC = 13.6 Hz), 137.5 (d, J PC = 9.5 Hz), 137.7 (d, J PC = 9.2 Hz), 138.4 (d, J PC = 2.3 Hz) _{, 139.3 (d, J PC =} 13.3 Hz), 140.1 (d, J PC = 33.3 Hz), 140.6 (d, J PC = 37.2 Hz), 237.6 (dd, J PC = 17.7 and 1.6 Hz), 239.4 (d , J _PC = 20.0 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ-10.4 (s), 95.8 (s).
EI-HRMS: theory _{(C 40 H 38 CrO 2 P} 2):. 664.1752 Found: 664.1753.
[[alpha]] _D ²⁴ -353 (c 0.10, EtOAc).

Reference Production Example 4-d
Preparation of (S)-(+)-[η ⁶ -1-Diphenylphosphino-2- (3-diphenylphosphino-2-phenylpropenyl) benzene-P] chromium (0) Dicarbonyl (3d ') Reference Preparation Example 4 as (R)-or (S)-[η ⁶ -1-bromo-2- (3-di-R-phosphino-2-R′-propenyl) benzene-P] chromium (0) as a dicarbonyl, (R) - or (S) - [η ⁶ -1- bromo-2- (3-diphenylphosphino-2-phenyl-propenyl) benzene -P] chromium (0) with a dicarbonyl 2d ', R _"2 PCl The following compound 3d ′ was obtained in a yield of 44% in the same manner as in using chlorodiphenylphosphine as
3d '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 3d ′ are shown in FIGS. 14-1 to 14-3.

¹ H NMR (C ₆ D ₆ ): δ 3.61 (dd, J = 14.5 and 12.5 Hz, 1 H), 4.08-4.16 (m, 1 H), 4.19-4.25 (m, 2 H), 4.72 (dd, J = 6.2 and 1.6 Hz, 1 H), 4.91 (t, J = 6.1 Hz, 1 H), 6.37 (d, J = 1.3 Hz, 3 H), 6.83-6.85 (m, 2 H), 6.94-7.18 (m, 15 H), 7.43-7.47 (m, 2H), 7.60-7.73 (m, 6H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 37.1 (dd, J _PC = 13.9 and 13.9 Hz), 80.6 (s), 85.9 (d, J _PC = 3.9 Hz), 91.7 (s), 91.9 (s), 92.0 (d , J PC = 13.3 Hz), 107.4 (dd, J PC = 25.3 and 2.8 Hz), 124.4 (dd, J PC = 10.8 and 5.4 Hz), 126.8 (s) , 127.7, 128.1 , 128.3, 128.5 (d, J PC = 8.7 Hz), 128.6 (s), 128.9 (d, J PC = 6.9 Hz), 129.0 (s), 129.1 (s), 129.6 (s), 129.6 (s), _{131.3 (d, J PC = 9.3} Hz), 133.4 (d, J PC = 20.3 Hz), 133.4 (d, J PC = 11.0 Hz), 135.3 (d, J PC = 20.7 Hz), 135.5 (d, J PC = 12.9 Hz), 139.2 (d , J PC = 13.1 Hz), 139.6 (d, J PC = 32.1 Hz), 141.1 (d, J PC = 39.5 Hz), 141.1 (d, J PC = 39.5 Hz), 141.8 (s), 144.4 (d, J PC = 5.2 Hz), 236.7 (d, J PC = 18.4 Hz), 239.0 (d, J PC = 20.7 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ-10.0 (s), 98.7 (s).
EI-HRMS: theory _{(C 41 H 32 CrO 2 P} 2):. 670.1283 Found: 670.1275.
[α] _D ¹⁸ + 351 (c 0.50, EtOAc).

Reference Production Example 4-e
(R) - (-) - [η 6 -1- diphenylphosphino-2- (3-diphenylphosphino-propenyl) benzene -P] chromium (0) in the production Reference Production Example 4 of dicarbonyl (3e ') ( R) - or (S) - [η ⁶ -1- bromo-2- (3-di -R- phosphino -2-R'- propenyl) benzene -P] chromium (0) dicarbonyl, (R) - Or (S)-[η ⁶ -1-bromo-2- (3-diphenylphosphinopropenyl) benzene-P] chromium (0) except using dicarbonyl 2a ′ and using chlorodiphenylphosphine as R ′ ′ ₂ PCl The following compound 3e ′ was obtained in exactly the same manner in a yield of 77%.
3e '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 3e ′ are shown in FIGS. 15-1 to 15-3.

¹ H NMR (C ₆ D ₆ ): δ 2.95-3.04 (m, 1 H), 3.39-3. 48 (m, 1 H), 4.05-4. 08 (m, 1 H), 4, 14 (t, J = 6.1 Hz, 1H), 4.67 (dd, J = 6.1 and 2.3 Hz, 1 H), 4.84 (t, J = 6.1 Hz, 1 H), 5.50-5.59 (m, 1 H), 6.16 (d, J = 11.2 Hz, 1 H), 7.03-7.20 (m, 12H), 7.37-7.42 (m, 2H), 7.58-7.71 (m, 6H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 31.0 (dd, J _PC = 14.2 and 11.4 Hz), 80.7 (s), 86.2 (d, J _PC = 3.9 Hz), 91.6 (s), _{91.8 (d, J PC = 14.1} Hz), 91.9 (s), 105.7 (dd, J PC = 25.9 and 3.4 Hz), 128.2, 128.3, 128.4, 128.8 (d, J PC = 6.6 Hz), 128.8 (s) _{, 129.0 (d, J PC =} 6.9 Hz), 129.0 (d, J PC = 1.8 Hz), 129.4 (d, J PC = 2.4 Hz), 129.7 (s), 129.7 (d, J PC = 2.7 Hz), _{131.3 (d, J PC = 9.2} Hz), 133.1 (d, J PC = 10.5 Hz), 133.2 (d, J PC = 19.7 Hz), 135.6 (d, J PC = 12.9 Hz), 135.6 (d, J PC = 21.0 Hz), 139.3 (d , J PC = 13.6 Hz), 140.2 (d, J PC = 32.5 Hz), 141.0 (d, J PC = 38.5 Hz), 237.0 (dd, J PC = 17.6 and 2.0 Hz) , 239.1 (d, J _PC = 20.3 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ-9.
EI-HRMS: theory _{(C 35 H 28 CrO 2 P} 2):. 594.0970 Found: 594.0968.
^{_{[α] D 22 -467 (c}} 0.50, benzene).

Reference Production Example 4-f
Preparation of (S)-(+)-[η ⁶ -1-Diphenylphosphino-2- (2-benzyl-3-diphenylphosphinopropenyl) benzene-P] chromium (0) Dicarbonyl (3f ') Preparation Example (R)-or (S)-[η ⁶ -1-bromo-2- (3-di-R-phosphino-2-R'-propenyl) benzene-P] chromium (0) as a dicarbonyl R) - or (S) - a [eta ^6-1-bromo-2- (3-diphenylphosphino-2-benzyl-propenyl) benzene -P] chromium (0) dicarbonyl 2f 'used, R "as ₂ PCl The following compound 3f 'was obtained in a yield of 59% in the same manner as in Example 1 except that chlorodiphenylphosphine was used.
3f '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 3f ′ are shown in FIGS. 16-1 to 16-3.

¹ H NMR (C ₆ D ₆ ): δ 2.94 (dd, J = 30.6 and 15.0, 2H), 3.20 (t, J = 13.6 Hz, 1H), 3.69-3.73 (m, 1H), 4.13-4.18 ( m, 2H), 4.65 (d, J = 4.9 Hz, 1 H), 4.90 (t, J = 5.4 Hz, 1 H), 5. 92 (s, 1 H), 6.86-7.16 (m, 17 H), 7.42-7.66 (m , 8H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 35.8 (dd, J _PC = 14.1 and 14.1 Hz), 47.7 (d, J _PC = 4.1 Hz), 80.5 (s), 86.4 (d, J _PC = 3.9 Hz), 91.7 (d, J _PC = 12.9 Hz), 91.8 (s), 91.9 (s), 107.9 (dd, J _PC = 25.7 and 3.1 Hz), 123.0 (dd, J _PC = 11.0 and 4.6) Hz), 126.7 (s), 128.2, 128.4, 128.6 (s), 128.8 (d, J _PC = 6.9 Hz), 128.9 (s), 129.0 (d, J _PC = 6.7 Hz), 129.6 (s), 129.6 (s) _{(d, J PC = 1.5 Hz} ), 131.0 (d, J PC = 9.2 Hz), 133.3 (d, J PC = 20.0 Hz), 133.4 (d, J PC = 10.7 Hz), 133.5 (d, J PC = 20.7 Hz), 135.6 (d, J _PC = 12.6 Hz), 138.3 (s), 139.3 (d, J _PC = 13.4 Hz), 139.5 (d, J _PC = 31.8 Hz), 140.9 (s), 141.4 (d) , J _PC = 39.5 Hz), 236.6 (d, J _PC = 16.6 Hz), 239.0 (d, J _PC = 20.8 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ-9.72 (s), 97.3 (s).
EI-HRMS: theory _{(C 42 H 34 CrO 2 P} 2):. 684.1439 Found: 684.1428.
[α] _D ²² + 400 (c 0.57, benzene).

Reference Production Example 4-g
(S)-(+)-[η ⁶ -1-bis (3,5-dimethylphenyl) phosphino-2- (3-diphenylphosphino-2-methylpropenyl) benzene-P] chromium (0) dicarbonyl ( Preparation of 3 g ′) In Reference Preparation Example 4, (R)-or (S)-[η ⁶ -1-bromo-2- (3-di-R-phosphino-2-R′-propenyl) benzene-P] chromium (0) As dicarbonyl, (R)-or (S)-[η ⁶ -1-bromo-2- (3-diphenylphosphino-2-methylpropenyl) benzene-P] chromium (0) dicarbonyl 2a ′ The following compound 3g ′ was obtained in a yield of 71% in exactly the same manner as in Example 1 except that chloro-3.5-dixylylphosphine was used as R ′ ₂ PCl.
3g '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 3g ′ are shown in FIGS. 17-1 to 17-3.

¹ H NMR (C ₆ D ₆ ): δ 1.39 (s, 3 H), 2.03 (s, 6 H), 2. 13 (s, 6 H), 3.06 (t, J = 13.4 Hz, 1 H), 3.69-3. 76 (m , 1H), 4.19-4.25 (m, 2H), 4.87-4.89 (m, 1H), 4.95 (t, J = 6.0 Hz, 1H), 6.06 (s, 1H), 6.73 (s, 1H), 6.80 ( s, 1 H), 7.01-7. 12 (m, 4 H), 7. 16-7. 25 (m, 4 H), 7. 39 (d, J = 8.0 Hz, 2 H), 7.64-7. 74 (m, 4 H).
^{13 C {1 H} NMR (} C 6 D 6): δ21.3 (s), 21.3 (s), 27.4 (d, J PC = 4.6 Hz), 37.2 (dd, J PC = 14.2 and 14.2 Hz), 80.6 (s), 86.1 (d , J PC = 4.1 Hz), 92.1 (s), 92.3 (d, J PC = 1.6 Hz), 92.6 (d, J PC = 14.3 Hz), 108.9 (dd, J PC = 26.6 and 2.8 Hz), 121.2 (dd, J PC = 11.2 and 5.3 Hz), 128.1, 128.3, 128.3, 128.4, 128.9 (s), 129.4 (s), 130.9 (s), 131.2 (d, J PC = 20.2 Hz), 131.3 (d, J PC = 8.8 Hz), 131.5 (s), 133.0 (d, J PC = 20.5 Hz), 133.2 (d, J PC = 10.8 Hz), 135.8 (d, J PC = 12.3 Hz _{), 138.1 (d, J PC} = 7.1 Hz), 138.3 (d, J PC = 2.3 Hz), 138.5 (d, J PC = 6.9 Hz), 139.0 (d, J PC = 12.8 Hz), 139.8 (d, J _PC = 32.3 Hz), 141.5 (d, J _PC = 38.4 Hz), 236.8 (d, J _PC = 17.6 Hz), 239.2 (d, J _PC = 20.8 Hz).
³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ-10.4 (s), 97.2 (s).
EI-HRMS theory _{(C 40 H 38 CrO 2 P} 2):. 664.1752 Found: 664.1752.
^{_{[α] D 25 +220 (c}} 0.57, CHCl 3).

Reference Production Example 4-h
Preparation of (S)-(+)-[η ⁶ -1-Diisopropylphosphino-2- (3-diphenylphosphino-2-methylpropenyl) benzene-P] chromium (0) dicarbonyl (3h ') Reference Preparation Example 4 as (R)-or (S)-[η ⁶ -1-bromo-2- (3-di-R-phosphino-2-R′-propenyl) benzene-P] chromium (0) as a dicarbonyl, (R) - or (S) - [η ⁶ -1- bromo-2- (3-diphenylphosphino-2-methyl-propenyl) benzene -P] chromium (0) with a dicarbonyl 2a ', R _"2 PCl The following compound 3h ′ was obtained in a yield of 74% in the same manner as in using chlorodiisopropylphosphine as
3h '
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 3h ′ are shown in FIGS. 18-1 to 18-3.

¹ H NMR (C ₆ D ₆ ): δ 0.75 (t, J = 7.3 Hz, 3 H), 0.89-1.02 (m, 6 H), 1.32-1. 38 (m, 6 H), 1.63-1. 82 (m, 2 H) , 2.96-3.03 (m, 1H), 3.21-3.27 (m, 1H), 4.28-4.31 (m, 2H), 4.88 (d, J = 6.2 Hz, 1 H), 5.08 (t, J = 6.0 Hz, 1 H) ), 6.02 (d, J = 1.3 Hz, 1 H), 6.98-7.16 (m, 6 H), 7.51-7.56 (m, 2 H), 7.63-7. 68 (m, 2 H).
¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 17.8 (d, J _PC = 1.8 Hz), 19.6 (d, J _PC = 15.6 Hz), 20.6 (d, J _PC = 15.7 Hz), 20.7 (d, J _PC = 13.6 Hz), 22.3 (d, J _PC = 23.3 Hz), 26.5 (d, J _PC = 18.3 Hz), 27.2 (d, J _PC = 4.1 Hz), 38.8 (dd, J _PC = 17.6 and 13.7 Hz), 79.6 (s) , 85.7 (d, J PC = 4.1 Hz), 89.8 (d, J PC = 30.0 Hz), 91.3 (s), 92.9 (d, J PC = 3.6 Hz), 110.7 (dd, J _PC = 26,9 and 2.8 Hz), 121.6 (dd, J PC = 11.4 and 4.5 Hz), 127.9, 128.4, 128.7 (s), 129.4 (s), 130.7 (d, J PC = 9.0 Hz _{), 133.7 (d, J PC} = 11.0 Hz), 137.9 (d, J PC = 2.8 Hz), 139.2 (d, J PC = 31.3 Hz), 142.0 (d, J PC = 39.5 Hz), 236.6 (d, J _PC = 16.2 Hz), 239.8 (d, J _PC = 21.8 Hz).
³¹ P { ¹ H}: NMR (C ₆ D ₆ ): δ 4.81 (s), 99.3 (s).
EI-HRMS theory _{(C 30 H 34 CrO 2 P} 2):. 540.1439 Found: 540.1439.
[α] _D ²⁶ + 171 (c 0.50, benzene).

  Compound 6 'obtained in Reference Production Example 1 described above, compounds 1a' to 1f 'obtained in Reference Production Examples 2-a to 2-f, obtained in Reference Production Examples 3-a to 3-f described above Yields of the selected compounds 2a 'to 2f' and compounds 3a 'to 3h' obtained in Preparation Examples 4-a to 4-h and the substituent R in (2-substituted allyl) phosphine used in each Preparation Example And R ′ and the substituent R ′ ′ in chloro-substituted phosphine (R′′PCl) are shown in the following table.

Example 1
The following synthesis scheme 3 shows the synthesis steps of the compounds 2 to 6 used in the present invention.

Example 1-1
eta ⁵ - preparation of bromo cyclopentadienyl manganese (I) tricarbonyl (2)
2
Conway, BG; A solution of Cp manganese tricarbonyl (1) (1.0 g, 4.9 mmol) in THF (30 mL) was cooled to −50 ° C. according to the description of Conway, BG; Rausch, MD Organometallics 1985, 4, 688, ⁿ BuLi (7.0 mL, 11.27 mmol, 1.6 M hexane solution) was added dropwise under a nitrogen atmosphere. The reaction solution was stirred for 15 minutes at −50 ° C. and then cooled to −70 ° C. Subsequently, a solution of 1,2-dibromotetrachloroethane (2.5 g, 7.8 mmol) in THF (2.0 mL) is added dropwise to the reaction solution, stirred at -70 ° C for 10 minutes, and then raised to 0 ° C over 1 hour. It warmed. After further stirring for 30 minutes at 0 ° C., the reaction was quenched with aqueous ammonium chloride solution. The reaction mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. Subsequently, it was filtered and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column (hexane / EtOAc = 20/1) to give the title compound in 79% yield as yellow crystals (1.1 g).

¹ H NMR (CDCl ₃ ): δ 4.96 (s, 1 H), 5.09 (s, 1 H), 5.41 (s, 1 H), 9. 78 (s, ¹ H).
¹³ C { ¹ H} NMR (CDCl ₃ ): δ 83.1, 83.4, 85.5, 88.3, 91.6, 186.6, 221.6.
IR (CHCl ₃ ): 62 627.7, 1685.5, 1846.5, 1944.9, 2031.6 cm ^-1 .
HRMS: theory _{(C 9 H 4 BrMnO 4)} :. 309.8673 Found: 309.8674.

Example 1-2
(±) - preparation of (eta ^{5-1-bromo-2-formyl-cyclopentadienyl)} manganese (I) tricarbonyl (3)
3
^N BuLi (1.1 mL, 1.77 mmol, 1.6 M solution in hexane) was added dropwise to a solution of 2,2,6,6-tetramethylpiperidine (300 μL, 1.77 mmol) in THF (1.0 mL) at 0 ° C. and stirred for 30 minutes did. This solution was added to a THF solution (15 mL) of Cp bromomanganese complex 2 (500 mg, 1.77 mmol) at -50 ° C., and stirred for 1 hour. The reaction solution was cooled to -70 ° C, and DMF (205 μL, 2.65 mmol) was added dropwise via a syringe. After stirring for 10 minutes at −70 ° C., the temperature was slowly raised to 0 ° C., and the reaction was quenched with aqueous ammonium chloride solution. The reaction mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column (hexane / EtOAc = 10/1) to give the title compound as brown crystals in 87% yield.

¹ H NMR (CDCl ₃ ): δ 4.96 (s, 1 H), 5.09 (s, 1 H), 5.41 (s, 1 H), 9. 78 (s, ¹ H).
¹³ C { ¹ H} NMR (CDCl ₃ ): δ 83.3 (s), 83.4 (s), 85.5 (s), 88.3 (s), 91.6 (s), 186.6 (s), 221.6 (s).
IR (CHCl ₃ ): 628 628, 1686, 1847, 1945, 2032 cm ^-1 .
HRMS: theory _{(C 9 H 4 BrMnO 4)} :. 309.8673 Found: 309.8674.
The ¹ H-NMR and b ¹³ C-NMR spectra of Compound 3 are shown in FIGS. 19-1 and 19-2.

Example 1-3
(±) - preparation of (eta ^{5-1-bromo-2-vinyl-cyclopentadienyl)} manganese (I) tricarbonyl (4)
4
_{MePPh 3 I (990 mg, 2.45} mmol) in THF suspension of ^{(15 mL), t BuOK (} 317 mg, 2.83 mmol) was added, the reaction mixture for 5 minutes, and stirred at room temperature. A THF solution (2.0 mL) of manganese complex 3 was added, and the mixture was further stirred at room temperature for 10 minutes. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column (hexane / EtOAc = 10/1) to give the title compound as oil in 72% yield.
The ¹ H-NMR and b ¹³ C-NMR spectra of the compound 4 are shown in FIGS. 20-1 and 20-2.

¹ H NMR (CDCl ₃ ): δ 4.76 (s, 1 H), 4. 90 (s, ¹ H), 4.9 (s, 1 H), 5. 34 (d, J = 8.8 Hz, 1 H), 5.61 (d, J = 14.4 Hz, 1 H), 6. 39 (dd, J = 8.8 Hz and 14.4 Hz, 1 H).
¹³ C { ¹ H} NMR (CDCl ₃ ): δ 76.8 (s), 82.0 (s), 82.9 (s), 86.7 (s), 99.3 (s), 117.5 (s), 127.3 (s), 224.0 (s).
IR (CHCl ₃ ): 628 628, 665, 1845, 1932, 2022, 3119 cm ^-1 .
HRMS: theory _{(C 10 H 6 BrMnO 3)} :. 309.8673 Found: 309.8674.

Example 1-4
(±) - preparation of (eta ^{5-1-bromo-2-vinyl-cyclopentadienyl)} (diphenyl methallyl phosphine) manganese (I) dicarbonyl (5)
5
(±) -manganese complex 4 (457 mg, 1.48 mmol) and (methallyl) diphenylphosphine (355 mg, 1.48 mmol) were dissolved in benzene (25 mL) under a nitrogen atmosphere. The reaction solution was irradiated with light for 24 hours using a mercury lamp. The orange reaction solution was filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column (hexane / EtOAc = 10/1) to give the title compound as pale yellow crystals (65%).
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 5 are shown in FIGS. 21-1 to 21-3.

¹ H NMR (CDCl ₃ ): δ 1.23 (s, 3 H), 3.16 (d, J = 7.6 Hz, 2 H), 3. 75 (s, 1 H), 4. 29 (s, 1 H), 4. 35 (s, ¹ H), 4.62 (s, 1 H), 4. 79 (s, 1 H), 5. 15 (d, J = 8.4 Hz, 1 H), 5. 34 (d, J = 14 Hz, 1 H), 6. 35 (dd, J = 8.4 Hz and 14 Hz, 1H), 7.40 (6H, s), 7.57-7.58 (m, 4H).
¹³ C { ¹ H} NMR (CDCl ₃ ): δ 24.3 (s), 43.0 (d, J _PC = 23.8 Hz), 78.3 (s), 82.4 (s), 84.5 (s), 85.3 (s), 95.4 (s), 115.2 (s), 117.2 (d, J _PC = 9.6 Hz), 128.3 (d, J _PC = 5.9 Hz), 129.0 (s), 129.8 (s), 132.4 (d, J _PC = 9.5 Hz), 132.6 (d, J PC = 9.5 Hz), 137.9 (d, J PC = 27.3 Hz), 138.3 (d, J PC = 27.3 Hz), 138.6 (s), 231.7 (d, J PC = 22.6 Hz ).
³¹ P { ¹ H} NMR (CDCl ₃ ): δ 86.3.
IR (CHCl ₃ ): 187 1872, 1934 cm ^-1 .
HRMS: theory _{(C 25 H 23 BrMnO 2 P} ):. 520.0000 Found: 520.0004.

Example 1-5
(±) - preparation of [(eta ^5-1-bromo-2- (3-diphenylphosphino-2-methyl-propenyl) cyclopentadienyl -P)] manganese (I) dicarbonyl (6)
6
(±) -Manganese complex 5 (888 mg, 1.7 mmol) and Grubbs-II catalyst (37 mg, 0.0425 mg) were dissolved in CH ₂ Cl ₂ (12 mL) under nitrogen atmosphere and stirred at 50 ° C. for 12 hours. The resulting brown solution was filtered and concentrated under reduced pressure. The crude product was purified by silica gel column (hexane / EtOAc = 10/1) to give the title compound as yellow crystals (95%).
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 6 are shown in FIGS. 22-1 to 22-3.

¹ H NMR (CDCl ₃ ): δ 1.58 (s, 1 H), 2. 95 (dd, J = 8.0, 11.2 Hz, 1 H), 3.1 ¹ (dd, J = 8.0, 11.2 Hz, 1 H), 3.99 (s, 1 H) ), 4.72-4.73 (m, 1 H), 4.87-4. 88 (m, 1 H), 5. 94 (s, 1 H), 7. 35-7. 49 (m, 10 H).
¹³ C { ¹ H} NMR (CDCl ₃ ): δ 27.1 (d, J _PC = 3.5 Hz), 35.1 (d, J _PC = 19 Hz), 74.6 (s), 80.9 (s), 81.8 (s) , 99.9 (s), 116.3 ( d, J PC = 10.3 Hz), 128.2 (s), 128.9 (s), 129. 7 (s), 131.8 (d, J PC = 10.7 Hz), 132.1 (d, J _PC = 9.5 Hz), 137.2 (s), 137.6 (s), 137.8 (s), 138.8 (s), 229.8 (d, J _PC = 20.2 Hz), 230.5 (d, J _PC = 20.2 Hz).
³¹ P { ¹ H} NMR (CDCl ₃ ): δ 109.7.
HRMS: theory _{(C 23 H 19 BrMnO 2 P} ):. 491.9687 Found: 491.9686.

Example 1-6
Optical resolution of (±)-[(η ⁵ -1-bromo-2- (3-diphenylphosphino-2-methylpropenyl) cyclopentadienyl-P)] manganese (I) dicarbonyl (6) Separately, hexane / isopropanol (9/1) mixed solvent was used as a mobile phase using Dairal Chiralcel OD (φ 20 mm).
(+) Body: [α] _D ²⁵ + 0.728 (c 0.5, CDCl ₃ ),
(-) Body: [α] _D ²¹ -3.4 (c 0.694, CDCl ₃ )

Example 1-7
(+) Or (-)-[(η ⁵ -1-bis- (3,5-dimethylphenyl) phosphino-2- (3-diphenylphosphino-2-methylpropenyl) cyclopentadienyl-P)) manganese (I) Dicarbonyl (7a) and (±) or (−)-[(η ⁵ -1-bis- (3,5-dimethylphenyl) phosphino-2- (3-diphenylphosphino-2-methylpropenyl)] Preparation of cyclopentadienyl-P)) manganese (I) dicarbonyl (7b)
(Wherein, R represents a 3,5-xylyl group or a phenyl group)

(+) Alternatively, (-)-Cp manganese complex 6 (150 mg, 0.3 mmol) is dissolved in THF (10 mL), and ^t BuLi (170 μL. 0.3 mmol, 1.77 M solution in pentane) in a nitrogen atmosphere, It was added dropwise at -78 ° C. After stirring for 30 minutes at −78 ° C., R ₂ PCl (R = 3,5-xylyl group or phenyl group) (1.3 eq.) Was added dropwise. The reaction solution was slowly warmed to room temperature over 1.5 hours, and quenched with aqueous ammonium chloride solution. The reaction mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column (hexane / benzene = 1/1) to give the title compound as yellow crystals.

(+) Or (-)-[(η ⁵ -1-bis- (3,5-dimethylphenyl) phosphino-2- (3-diphenylphosphino-2-methylpropenyl) cyclopentadienyl-P)) manganese (I) Dicarbonyl (7a)
7a
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 7a are shown in FIGS. 23-1 to 23-3.

¹ H NMR (CDCl ₃ ): δ 1.42 (s, 3H), 2.18 (s, 3H), 2.28 (s, 3H), 2.99 (t, J = 10.0 Hz, 1 H), 3.65-3. 69 (m, 1 H), 4. 13 (s, 1 H), 4. 34 (s, 1 H), 4. 79 (s, 1 H), 5. 86 (s, 1 H), 6. 89 (d, J = 6.4 Hz, 1 H), 6. 92 (d, J = 6.0 Hz, 1 H), 6.99 (d, J = 6.4 Hz, 1 H), 7. 35-7.41 (m, 4 H), 7.43-7. 46 (m, 2 H), 7. 50- 7.53 (m, 2H), 7.56-7.60 (m, 2H).
¹³ C { ¹ H} NMR (CDCl ₃ ): δ 21.4 (d, J _PC = 25 Hz), 27.1 (d, J _PC = 3.5 Hz), 36.2 (m), 77.4 (s), 79.9 (d, J _PC = 3.5 Hz), 82.0 (s), 83.6 (d, J _PC = 4.8 Hz), 88.3 (d, J _PC = 11.9 Hz), 106.6 (d, J _PC = 25.0 Hz), 117.2 (d, J _{PC = 11.9 Hz), 128.0 (} d, J PC = 9.5 Hz), 128.3 (d, J PC = 8.3 Hz), 129.3 (s), 129.6 (s), 130.0 (d, J PC = 6.0 Hz), 130.1 (s), 131.1 (s) , 131.3 (d, J PC = 9.5 Hz), 132.6 (d, J PC = 8.3 Hz), 132.8 (s), 135.9 d, J PC = 8.3 Hz), 137.2 (s) , 137.4 (s), 137.7 ( d, J PC = 6.0 Hz), 137.8 (d, J PC = 8.4 Hz), 139.1 (d, J PC = 7.1 Hz), 139.3 (s), 139.5 (s), 228.6 (d, J _PC = 20.2 Hz), 231.2 (d, J _PC = 22.6 Hz).
³¹ P { ¹ H} NMR (CDCl ₃ ): δ-21.7, 106.8.
IR (CHCl ₃ ): 694 694, 750, 1434, 1873, 1938, 3402 cm ⁻¹ .
HRMS: theory _{(C 39 H 37 MnO 2 P} 2):. 654.1649 Found: 654.1658.
^{_{[α] D 26 +135.1 (c}} 0.5, CDCl 3), [α] D 25 -162.8 (c 0.5, CDCl 3).

(±)-[(η ⁵ -1-diphenylphosphino-2- (3-diphenylphosphino-2-methylpropenyl) cyclopentadienyl-P)] manganese (I) dicarbonyl (7b)
7b
The ¹ H-NMR, ¹³ C-NMR and ³¹ P-NMR spectra of the compound 7b are shown in FIGS. 24-1 to 24-3.

¹ H NMR (CDCl ₃ ): δ 1.44 (s, 3 H), 3.01 (t, J = 13.0 Hz, 1 H), 3. 60-3. 65 (m, 1 H), 4. 13 (s, 1 H), 4.32 (s, 1 H), 4.82 (s, 1 H), 5.81 (s, 1 H), 7. 27-7. 35 (m, 1 H) 12H), 7.41-7.43 (m, 4H), 7.52-7.57 (m, 4H).
¹³ C { ¹ H} NMR (CDCl ₃ ): δ 27.1 (d, J _PC = 3.5 Hz), 35.8 (m), 79.9 (s), 82.8 (d, J _PC = 26.1 Hz), 87.9 (d, J _PC = 10.7 Hz), 106.3 (d, J _PC = 23.8 Hz), 117.0 (d, J _PC = 10.7 Hz), 128.0 (s), 128.1 (s), 128.3 (s), 128.4 (d, J _PC = 6.0 Hz), 129. 4 (s), 129.7 (s), 131.2 (d, J _PC = 9.5 Hz), 132.3 (d, J _PC = 19.0 Hz), 132.7 (d, J _PC = 9.5 Hz), 135.2 (d, J _PC = 20.3 Hz), 136.1 (d, J _PC = 8.3 Hz), 137.1 (s), 137.5 (s), 138.9 (s), 139.3 (s), 139.7 (d, J _PC = 10.7 Hz).
³¹ P { ¹ H} NMR (CDCl ₃ ): δ-21.2, 106.2.
IR (CHCl ₃ ): 628 628, 665, 1845, 1932, 2022, 3119 cm ^-1 .
HRMS: theory _{(C 35 H 29 BrMnO 2 P} 2):. 598.1023 Found: 598.1022.

Example 2
Rhodium-Catalyzed Asymmetric 1,4-Addition of 4-Methylphenylboronic Acid to 2-Cyclohexenone
[RhCl (η ² -C ₂ H ₄ ) ₂ ] ₂ (2.4 mg, 6.3 μmol) and (R)-(+)-or (S)-(-)-7a (13 μmol) synthesized in Example 1 The dioxane solution (1 mL) was stirred at room temperature under nitrogen atmosphere for 1 hour. To this solution was added KOH (1.25 M, 0.1 mL, 0.13 mmol) and stirred for 5 minutes. 4-Methylphenylboronic acid (102 mg, 0.75 mmol) and 2-cyclohexanone (24 mg, 0.25 mmol) were added to this solution. After stirring at 50 ° C. for 9 hours, the reaction solution was concentrated under reduced pressure. The residue was purified by silica gel column (hexane / EtOAc = 4/1) to give optically active 3- (p-methylphenyl) cyclohexanone in a yield of 99% or more as a colorless oil. The optical purity (ee) of the product was determined to be 99.9% or higher by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Example 3
Rhodium-catalyzed asymmetric 1,4-addition reaction of p-methoxyphenylboronic acid to 2-cyclohexenone Example 2 was repeated except that 4-methylphenylboronic acid in Example 2 was replaced by p-methoxyphenylboronic acid. In exactly the same manner, optically active 3- (p-methoxyphenyl) cyclohexanone was obtained in 98% yield as a colorless oil. The optical purity (ee) of the product was determined to be 99.8% by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Example 4
Rhodium-catalyzed asymmetric 1,4-addition reaction of p-trifluoromethylphenylboronic acid to 2-cyclohexenone With the exception of replacing 4-methylphenylboronic acid with p-trifluoromethylphenylboronic acid in Example 2, In exactly the same manner as in Example 2, optically active 3- (p-trifluoromethylphenyl) cyclohexanone was obtained in a yield of 99% or more as a colorless oil. The optical purity (ee) of the product was determined to be 99.2% by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Example 5
Rhodium-catalyzed asymmetric 1,4-addition reaction of p-fluorophenylboronic acid to 2-cyclohexenone Example 2 and Example 2 except that 4-methylphenylboronic acid in Example 2 was replaced by p-fluorophenylboronic acid. In exactly the same manner, optically active 3- (p-fluorophenyl) cyclohexanone was obtained as a colorless oil in a yield of 99% or more. The optical purity (ee) of the product was determined to be 99.6% by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Example 6
Rhodium-catalyzed asymmetric 1,4-addition reaction of o-methylphenylboronic acid to 2-cyclohexenone Example 2 was repeated except that 4-methylphenylboronic acid in Example 2 was replaced by o-methylphenylboronic acid. In exactly the same manner, optically active 3- (o-methylphenyl) cyclohexanone was obtained as a colorless oil in a yield of 99% or more. The optical purity (ee) of the product was determined to be 99.9% yield by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Example 7
Rhodium-Catalyzed Asymmetric 1,4-Addition Reaction of Phenylboronic Acid to 3-Pent-2-one The 4-methylphenylboronic acid in Example 2 is replaced with phenylboronic acid, and 2-cyclohexenone is 3-pente-2 The optically active 4-phenylpentan-2-one was obtained as a colorless oil in a yield of 99% in the same manner as in Example 2 except that -on was substituted. The optical purity (ee) of the product was determined to be 98% by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Example 8
Rhodium-Catalyzed Asymmetric 1,4-Addition Reaction of Phenylboronic Acid to 3-Hept-2-one The 4-methylphenylboronic acid in Example 2 is replaced with phenylboronic acid, and 2-cyclohexenone is 3-hepte-2 The optically active 4-phenylhept-2-one was obtained as a colorless oil in a yield of 92% in the same manner as in Example 2 except that -ON was substituted. The optical purity (ee) of the product was determined to be 99% by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Example 9
Rhodium-Catalyzed Asymmetric 1,4-Addition Reaction of Phenylboronic Acid to 3-None-2-one The 4-methylphenylboronic acid in Example 2 is replaced with phenylboronic acid and 2-cyclohexenone 3-none-2 The optically active 4-phenylnon-2-one was obtained in a yield of 77% as a colorless oil in the same manner as in Example 2 except that -ON was substituted. The optical purity (ee) of the product was determined to be 99.8% by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Comparative Example 1
Rhodium-catalyzed asymmetric 1,2-addition reaction of phenylboronic acid to p-chlorobenzaldehyde N-tosylimine
[RhCl (η ² -C ₂ H ₄ ) ₂ ] ₂ (3.9 mg, 10 μmol) and (R)-(+)-or (S)-(-)-3 '(12 mg, 20 μmol)) Of dioxane solution (1 mL) was stirred at room temperature under nitrogen atmosphere for 1 h. To this solution was added p-chlorobenzaldehyde N-tosylimine (58.6 mg, 0.200 mmol), phenylboroxine (62.3 mg, 0.200 mmol), an aqueous KOH solution (1.25 M, 32 mL, 40 μmol). After stirring at 60 ° C. for 12 hours, the reaction solution was concentrated under reduced pressure. The residue was purified by silica gel column (hexane / EtOAc = 5/1) to give optically active N-[(p-chlorophenyl) phenylmethyl] tosylamide as colorless crystals in 98% yield. The optical purity (ee) of the product was determined to be 93% by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Comparative example 2
Rhodium-catalyzed asymmetric 1,4-addition reaction of 4-methylphenylboronic acid to 2-cyclohexenone Using p-methylphenylboronic acid instead of phenylboroxine in Comparative Example 1, p-chlorobenzaldehyde N-tosylimine An optically active 3- (p-methylphenyl) cyclohexanone was obtained as a colorless oil in a yield of 99% or more in the same manner as in Comparative Example 1 except that 2-cyclohexenone was used instead. The optical purity (ee) of the product was determined to be 98.4% by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Comparative example 3
Rhodium-catalyzed asymmetric 1,4-addition reaction of p-trifluoromethylphenylboronic acid to 2-cyclohexenone Except for using p-trifluoromethylphenylboronic acid instead of p-methylphenylboronic acid in Comparative Example 2. Using the same method as Comparative Example 2, optically active 3- (p-trifluoromethylphenyl) cyclohexanone was obtained as a colorless oil in a yield of 95%. The optical purity (ee) of the product was determined to be 97% by chiral HPLC analysis.
The HPLC chart is shown in FIG.

Comparative example 4
Rhodium-catalyzed asymmetric 1,4-addition reaction of phenylboronic acid to 3-pent-2-one Using phenylboronic acid in place of p-methylphenylboronic acid in Comparative Example 2, 3 in place of 2-cyclohexenone The same procedure as in Comparative Example 2 was followed except that -Pent-2-one was used. In this reaction, (R) - (-) - [η 6 -1- diphenylphosphino-2- (3-diphenylphosphino-2-methyl-propenyl) benzene -P] chromium (0) dicarbonyl (3a ') The optically active (R) -4-phenyl-3-pent-2-one was obtained as a colorless oil in 31% yield. The optical purity (ee) of the product was determined to be 57% by chiral HPLC analysis. Further, in this reaction, (S) - (+) - [η 6 -1- bis (3,5-dimethylphenyl) phosphino-2- (3-diphenylphosphino-2-methyl-propenyl) benzene -P] Chromium (0) When dicarbonyl (3 g ′) was used, optically active (S) -4-phenyl-3-pent-2-one was obtained as a colorless oil at a yield of 34%. The optical purity (ee) of the product was determined to be 88% by chiral HPLC analysis.
These HPLC charts are shown in FIG.

Comparative example 5
Rhodium-catalyzed asymmetric 1,4-addition reaction of phenylboronic acid to 3-non-2-one With phenylboronic acid in place of p-methylphenylboronic acid in Comparative Example 2, 3 in place of 2-cyclohexenone Comparative Example 2 was carried out in exactly the same manner as in Comparative Example 2 except that nonone-2-one was used. In this reaction, (R) - (-) - [η 6 -1- diphenylphosphino-2- (3-diphenylphosphino-2-methyl-propenyl) benzene -P] chromium (0) dicarbonyl (3a ') The optically active (R) -4-phenylnon-2-one was obtained as a colorless oil in 13% yield. The optical purity (ee) of the product was determined to be 58% by chiral HPLC analysis. Also, in this reaction, (S)-(+)-[[ ⁶ -1-bis (3,5-dimethylphenyl) phosphino-2- (3-diphenylphosphino-2-methylpropenyl) benzene-P] chromium (0) When dicarbonyl (3 g ′) was used, optically active (S) -4-phenylnon-2-one was obtained as a colorless oil in 43% yield. The optical purity (ee) of the product was determined to be 88% by chiral HPLC analysis.
These HPLC charts are shown in FIG.

Comparative example 6
Rhodium-Catalyzed Asymmetric 1,4-Addition Reaction of 4-Phenylboronic Acid to N-Benzylmaleimide
A solution of [Rh (OH) cod] ₂ (1.4 mg, 3.1 μmol) and 3 '(6.9 μmol) in ether (1 mL) was stirred at room temperature for 10 minutes under a nitrogen atmosphere. To this was added H ₂ O (0.5 mL) and further stirred for 10 minutes. To this mixed solution was added phenylboronic acid (46 mg, 0.38 mmol) and N-benzylmaleiimide (24 mg, 0.13 mmol), and the mixture was stirred at -20.degree. C. for 3 hours. The reaction solution was heated to 0 ° C. and stirred for further 12 hours. The reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column (hexane / EtOAc = 3/1) to give optically active N-benzyl-3-phenylsuccinimide as colorless crystals. The optical purity (ee) of the product was determined by chiral HPLC analysis. In this reaction, (R) - (-) - [η 6 -1- diphenylphosphino-2- (3-diphenylphosphino-2-methyl-propenyl) benzene -P] chromium (0) dicarbonyl (3a ') The optically active (R) -N-benzyl-3-phenylsuccinimide was obtained as a colorless oil in 85% yield. The optical purity (ee) of the product was determined to be 81% by chiral HPLC analysis. Further, in this reaction, (S) - (+) - [η 6 -1- bis (3,5-dimethylphenyl) phosphino-2- (3-diphenylphosphino-2-methyl-propenyl) benzene -P] Chromium (0) When dicarbonyl (3 g ′) was used, optically active (S) -N-benzyl-3-phenylsuccinimide was obtained as a colorless oil in 83% yield. The optical purity (ee) of the product was determined to be 94% by chiral HPLC analysis.
These HPLC charts are shown in FIG.

  As described above, as described in the examples, the optically active asymmetric ligand according to the present invention can be easily optically resolved by commercially available chiral HPLC, and each optically active substance can be transition metal catalyst 1,4-diester according to the purpose. It can be used as an asymmetric ligand for addition reaction.

The results of the chiral ligand, the rhodium catalyst and the rhodium catalyst asymmetric 1,4-addition reaction in the above Examples 2 to 9 and Comparative Examples 1 to 6 are summarized in Table 2 below.

From the results of Examples 2 to 6 described above, by using the optically active asymmetric ligand according to the present invention, it is possible to obtain a compound having a high yield and an optical purity for the desired optically active 1,4-adduct. It turned out that it could be obtained selectively.
Also, at that time, high yield and optical purity of optically active 1,4-adducts without being greatly affected by the electron donating property or electron withdrawing property of Ar group in ArB (OH) ₂ used It turned out that it is possible to selectively obtain the compound of

  From the results of Examples 7 to 9, not only cyclic enone compounds but also aliphatic enone compounds, ie, 3-pent-2-one, 3 can be obtained by using the optically active asymmetric ligand according to the present invention. -Also for hept-2-one and 3-non-2-one, by using the optically active asymmetric ligand according to the present invention, the objective optically active 1,4-adduct is obtained in high yield. It has been found that compounds of rate and optical purity can be obtained selectively.

Example 10
Without using (R)-(+)-or (S)-(-)-7a in Example 2, the following formula:
According to the above, the 1,4-addition reaction to 2-cyclohexenone was carried out at 50 ° C. for 12 hours, but no addition reaction to 2-cyclohexenone occurred.
Therefore, the planar asymmetric ligand for transition metal catalyzed asymmetric 1,4-addition reaction according to the present invention has not only its mechanism completely elucidated, but it has not only a characteristic as a simple planar asymmetric ligand It is thought that it is also involved in the increase of the activity of the transition metal catalyst.

By using an asymmetric ligand for the transition metal 1,4-addition reaction according to the invention:
(R) -Tolterodine which is a therapeutic agent for the accumulation of urine, (S) -flavanone having an antioxidant action, (S) -pinostrobin having an antiviral activity and (R) -fence which is an antiepileptic drug It is considered that a compound having high optical purity of a pharmaceutical having an asymmetric carbon such as succinimide or a precursor thereof or a novel pharmaceutical can be produced in a high yield.

  According to the present invention, by using together with a transition metal catalyst, transition metal 1,4-addition with high yield and high optical purity to various enone compounds including not only cyclic enone compounds but also aliphatic enone compounds It is possible to provide an asymmetric ligand for reaction, and to enable easy and inexpensive production of a pharmaceutical having an asymmetric carbon or a precursor thereof or other useful compound.

Claims (8)

The following general formula (7):
(7)
(Wherein R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group, and R ′ is optionally substituted with a hydrogen atom or an aryl group be optionally substituted with or unprotected _C 1 -C ₄ alkyl or _C 1 -C ₄ alkyl group is an aryl group, R _"is, C 1 -C ₄ alkyl or _C 1 -C ₄ An aryl group which may be optionally substituted with an alkyl group)
(+) Or (−)-((η ⁵ 1-phosphino-2-propenyl) cyclopentadienyl-P) manganese (I) dicarbonyl compound represented by   In the general formula (7), the R is an isopropyl group, a phenyl group or a 3,5-xylyl group, the R ′ is a hydrogen atom, a methyl group, an isopropyl group, a phenyl group or a benzyl group, and the R ′ ′ is The compound according to claim 1, wherein is an isopropyl group, a phenyl group or a 3,5-xylyl group.   In the general formula (7), R is a phenyl group or 3,5-xylyl group, R 'is a methyl group or isopropyl group, and R "is a phenyl group or 3,5-xylyl group The compound according to claim 1 or 2. Formula (7) as described in any one of Claims 1-3.
(7)
(Wherein R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group, and R ′ is optionally substituted with a hydrogen atom or an aryl group be optionally substituted with or unprotected _C 1 -C ₄ alkyl or _C 1 -C ₄ alkyl group is an aryl group, R _"is, C 1 -C ₄ alkyl or _C 1 -C ₄ An aryl group which may be optionally substituted with an alkyl group)
In represented by, (+) or (-) - a ((eta ^{5-1-phosphino-2-propenyl)} cyclopentadienyl -P) manganese (I) dicarbonyl compounds, used in the transition metal catalyzed asymmetric reactions A method of using the compound of formula (7) as a planar asymmetric ligand for transition metal catalyzed asymmetric reactions, characterized in that:   The transition metal catalyzed asymmetric reaction is a transition metal catalyzed asymmetric allylic amination, asymmetric allylic thioetherification, asymmetric allylic alkynylation or asymmetric Suzuki-Miyaura cross coupling reaction; organoboron Asymmetric 1,4-addition reaction of acid to enone compound or asymmetric 1,2-addition reaction to imine compound; Asymmetric 1,4-addition reaction of organic zinc compound to enone compound or imine compound Or an asymmetric 1,2-addition reaction of an organic titanium compound to an enone compound or an asymmetric 1,2-addition reaction to an imine compound. Method of use as an asymmetric ligand for asymmetric reactions.   The use method as an asymmetric ligand for asymmetric reaction according to claim 4 or 5, wherein the transition metal catalyst is rhodium, palladium or iridium. A transition with (+) or (-) (( ⁵ 5-1-phosphino-2-propenyl) cyclopentadienyl-P) manganese (I) dicarbonyl compound according to any one of claims 1 to 3 A catalyst composition comprising a metal salt or transition metal complex precursor. The following equation (1):
(1)
The lithiation agent and the brominating agent are reacted with cyclopentadienyl manganese tricarbonyl (1) represented by the formula (2) in an aprotic organic solvent,
(2)
An η ⁵ -bromocyclopentadienyl manganese (I) tricarbonyl compound represented by the formula is obtained, which is reacted with lithium amide and dimethylformamide in an aprotic organic solvent to obtain a compound of the formula (3):
(3)
In represented (±) - give (eta ^{5-1-bromo-2-formyl-cyclopentadienyl)} manganese (I) tricarbonyl compound in an aprotic organic solvent thereto, methyl iodide triphenylphosphonium and The organic base is reacted, and the formula (4):
(4)
In represented (±) - give (eta ^{5-1-bromo-2-vinyl-cyclopentadienyl)} manganese (I) tricarbonyl compound, in benzene to the following formula:
(Wherein, R 'represents a hydrogen atom, optionally substituted by C ₁ optionally -C ₄ alkyl or C ₁ -C ₄ alkyl optionally substituted in the aryl group with a group with an aryl group , R ′ ′ is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group)
The allyl phosphine compound represented by is reacted under light irradiation using a mercury lamp as a light source, and the formula (5):
(5)
(Wherein, R 'represents a hydrogen atom, optionally substituted by C ₁ optionally -C ₄ alkyl or C ₁ -C ₄ alkyl optionally substituted in the aryl group with a group with an aryl group , R ′ ′ is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group)
In represented (±) - give (eta ^{5-1-bromo-2-vinyl-cyclopentadienyl)} allyl phosphine manganese (I) dicarbonyl compounds, which under inert gas, aprotic organic solvent metathesis By the olefin metathesis reaction in the presence of a catalyst, formula (6):
(6)
(Wherein, R 'represents a hydrogen atom, optionally substituted by C ₁ optionally -C ₄ alkyl or C ₁ -C ₄ alkyl optionally substituted in the aryl group with a group with an aryl group , R ′ ′ is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group)
In represented (±) - give (eta ^5-1-bromo-2- (3-phosphino-1-propenyl) cyclopentadienyl -P) manganese (I) dicarbonyl compounds,
Optically divide this,
(+) - (eta ^5-1-bromo-2- (3-phosphino-1-propenyl) cyclopentadienyl -P) manganese (I) dicarbonyl compounds, and (-) - (eta ^5-1-bromo -2- (3-Phosphino-1-propenyl) cyclopentadienyl-P) manganese (I) dicarbonyl compounds are obtained, which, in an aprotic organic solvent,
R ₂ PCl
(Wherein, R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group)
Are each reacted to give formula (7):
(7)
(Wherein R is an aryl group optionally substituted with a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkyl group, and R ′ is optionally substituted with a hydrogen atom or an aryl group be optionally substituted with or unprotected _C 1 -C ₄ alkyl or _C 1 -C ₄ alkyl group is an aryl group, R _"is, C 1 -C ₄ alkyl or _C 1 -C ₄ An aryl group which may be optionally substituted with an alkyl group)
In represented by, (+) or (-) - method for producing ((eta ^{5-1-phosphino-2-propenyl)} cyclopentadienyl -P) manganese (I) dicarbonyl compounds.