JP5278937B2 - Method for producing optically active secondary alcohol - Google Patents

Description

  The present invention relates to a method for producing an optically active secondary alcohol, and more specifically, an optically active secondary alcohol is obtained by allowing an olefin, particularly styrene, to coexist in the presence of an optically active cobalt (II) complex catalyst. Regarding the method.

So far, asymmetric reduction methods and kinetic optical resolution methods have been reported as methods for producing optically active secondary alcohols.
The asymmetric reduction method is a method of enantioselectively reducing a raw material ketone in the presence of a catalyst. This method requires a number of experiments to select a catalyst, and if there are other functional groups that undergo a reduction reaction in the same molecule, there is a problem that it must be distinguished from the intended reaction. (See Patent Document 1).

On the other hand, in the optical resolution method using an enzyme, racemic optical resolution is performed based on a reaction limited to a secondary alcohol, and the operation is safe. However, since the biological reaction is utilized, the substrate specificity is high, the volume Low efficiency has been pointed out as a problem (see Patent Document 2).
In addition, optical resolution methods based on oxidation reactions using palladium (II) complexes have been reported (see Non-Patent Documents 1 and 2), which are optically active ligands derived from natural (-)-spartein. Therefore, there is a problem that only one optically active substance can be produced. Further, palladium is one of rare metals, and development of alternative technology is strongly desired.
JP-A-8-310981 Japanese Patent Laid-Open No. 3-259094 Mandal, SK; Jensen, DR; Pugsley, JR; Sigman, MSJ Org. Chem. 2003, 68, 4600-4603. Bagdanoff. JT; Stoltz, BM Angew. Chem. Int. Ed. 2004, 43, 353-357.

  The objective of this invention is providing the manufacturing method of the optically active secondary alcohol which solved the said problem in the conventional manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventors have determined that a racemic secondary alcohol can be converted into oxygen molecules in the presence of a catalytic amount of an optically active cobalt (II) complex catalyst in the presence of olefins, particularly styrenes. It was found that only one of the optical isomers was selectively oxidized with oxygen and converted into the corresponding ketone, and the unreacted secondary alcohol was recovered with high optical purity. It came to be completed.

That is, the present invention
1. The racemic secondary alcohol is oxidized with oxygen molecules in a solvent in the presence of an olefin in the presence of a catalytic amount of an optically active cobalt (II) complex catalyst to recover unreacted secondary alcohol. A method for producing an optically active secondary alcohol.

［式中、Ｒ¹とＲ²は異なる基であり、それぞれ、水素原子、直鎖もしくは分岐状のアルキル基、またはアリール基であり、これらは置換基を有していてもよく、２個のＲ¹同士または２個のＲ²同士は、相互に結合して環を形成してもよく、Ｒ³、Ｒ⁴およびＲ⁵は、同一でも異なっていてもよく、水素原子、直鎖もしくは分岐状のアルキル基、アリール基、−ＣＯＲ’（ここでＲ’は水素原子、直鎖もしくは分岐状のアルキル基、シクロアルキル基、アダマンチル基、またはアリール基であり、これらは置換基を有していてもよく、置換もしくは非置換のベンゼン環と縮合していてもよい）または−ＣＯ₂Ｒ”（ここでＲ”は水素原子、直鎖もしくは分岐状のアルキル基、シクロアルキル基、アダマンチル基、またはアリール基であり、これらは置換基を有していてもよく、置換もしくは非置換のベンゼン環と縮合していてもよい）であり、これらは置換基を有していてもよい］
で表される化合物である、上記１．に記載の製造方法。 2. The optically active cobalt (II) complex catalyst has the formula:

[Wherein, R ¹ and R ² are different groups, each of which is a hydrogen atom, a linear or branched alkyl group, or an aryl group, which may have a substituent, R ^{1 s} or two R ^{2 s} may be bonded to each other to form a ring, and R ³ , R ^4, and R ⁵ may be the same or different, and may be a hydrogen atom, linear or branched An alkyl group, an aryl group, or —COR ′ (where R ′ is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an adamantyl group, or an aryl group, and these have a substituent. Or may be condensed with a substituted or unsubstituted benzene ring) or —CO ₂ R ″ (where R ″ is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an adamantyl group, Or an aryl group, these May have a substituent group, is also be) fused with a substituted or unsubstituted benzene ring, which may have a substituent]
The compound represented by the above 1. The manufacturing method as described in.

3. One of R ¹ and R ² is hydrogen, the other is an aryl group, and R ³ , R ⁴ and R ⁵ may be the same or different, and may be a hydrogen atom, linear or branched alkyl A group, —COR ′ (where R ′ is a linear or branched alkyl group or aryl group) or —CO ₂ R ″ (where R ″ is a linear or branched alkyl group, cycloalkyl group or 2. an adamantyl group). The manufacturing method as described in.

4). One of R ¹ and R ² is hydrogen, the other is a mesityl group, R ³ is a hydrogen atom, R ⁴ and R ⁵ may be the same or different, and methyl, acetyl, mesi 3. The above 3, which is tilcarbonyl, ethoxycarbonyl, cyclohexyloxycarbonyl, or (2-adamantyl) oxycarbonyl. The manufacturing method as described in.

  5. The optically active cobalt (II) complex catalyst is [N, N′-bis (2-ethoxycarbonyl-3-oxobutylidene)-(1S, 2S) -dimesitylethylenediaminato] cobalt (II), [N, N '-Bis (2-cyclohexyloxycarbonyl-3-oxobutylidene)-(1S, 2S) -dimesitylethylenediaminato] cobalt (II), and [N, N′-bis (2- (2-adamantyl) oxy 3. Carbonyl-3-oxobutylidene)-(1S, 2S) -dimesitylethylenediaminato] cobalt (II) above. The manufacturing method as described in.

6). In the above 1., the olefin is styrene optionally substituted with an electron withdrawing group. ~ 5. The manufacturing method as described in.
7). 5. The olefin as described above, wherein the olefin is styrene or p-chlorostyrene. The manufacturing method as described in.

（式中、Ｒ⁶およびＲ⁷は異なる有機基であり、ここで該有機基は互いに結合してもよい）で表される化合物である、上記１．〜７．に記載の製造方法。 8). The racemic secondary alcohol has the formula:

Wherein R ⁶ and R ⁷ are different organic groups, wherein the organic groups may be bonded to each other. ~ 7. The manufacturing method as described in.

9. R ⁶ and R ⁷ are each a linear or branched alkyl group, a linear or branched alkenyl group or an aryl group, which may have a substituent, or R ⁶ and R 7 ⁷ bond to each other to form a cycloalkyl group, which may contain a hetero atom, may have a substituent, may contain a spiro carbon to form a spiro ring, Or it may be condensed with an unsubstituted benzene ring. The manufacturing method as described in.
10. Either one of R ⁶ and R ⁷ is an aryl group and the other is a linear or branched alkyl group, or R ⁶ and R ⁷ are bonded to each other to form a cycloalkyl group; This is fused to a substituted or unsubstituted benzene ring, above 9. The manufacturing method as described in.

According to the method of the present invention, the above problems in the asymmetric reduction method, the optical resolution method using an enzyme, and the optical resolution method based on an oxidation reaction using a palladium (II) complex are solved. The reaction proceeds under relatively mild conditions, and the secondary alcohol can be recovered with high optical purity.
In the optical resolution method, control of the conversion rate of the reaction is important. However, in the conventional method, it is necessary to appropriately stop the reaction while sequentially monitoring the progress of the reaction. According to the invention of this reaction, the conversion rate of the reaction can be easily and arbitrarily controlled by adjusting the amount of olefin used.

Hereinafter, the present invention will be described in detail.
The present invention is considered to be based on the reaction mechanism exemplified below.

  That is, in the reaction of the present invention, the racemic secondary alcohol serves as a substrate for the oxidation reaction by the optically active cobalt (II) catalyst, and the olefin acts as an oxygen acceptor, whereby one optical isomer of the racemic secondary alcohol. Is converted to the corresponding ketone, and the other optical isomer can be obtained.

で表され、Ｒ¹とＲ²は異なる基であり、それぞれ、水素原子、直鎖もしくは分岐状のアルキル基、またはアリール基であり、これらは置換基を有していてもよい。 In the method of the present invention, the optically active cobalt (II) complex used as a catalyst preferably has the formula:

R ¹ and R ² are different groups, each of which is a hydrogen atom, a linear or branched alkyl group, or an aryl group, and these may have a substituent.

In the present specification, the “linear or branched alkyl group” refers to C ₁ such as methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, sec-butyl group, n-butyl group and the like. _{-12 A} linear or branched alkyl group or the like.
The "aryl group" in the present specification, for example, a phenyl group, a substituted phenyl group, for example mesityl group, p- methoxyphenyl group, p- chlorophenyl group, p- fluorophenyl group, C _6, such as a naphthyl group, substituted naphthyl group _{-18 means an} aryl group.

In the present specification, the “substituent” may be the same or different, for example, a C _1-12 linear or branched alkyl group, a C _1-6 linear or branched alkoxy group such as a methoxy group or An ethoxy group or a halogen atom such as fluorine, chlorine, or bromine is not limited thereto. Any number, preferably 1 to 3, of these substituents can be substituted at any position.

Further, two R ^{1 s} or two R ^{2 s} may be bonded to each other to form a ring. For example, they may be bonded to each other via a group such as — (CH ₂ ) ₄ —. A ring such as a 6-membered ring may be formed.
Further, R ³ , R ⁴ and R ⁵ may be the same or different and are each a hydrogen atom, a linear or branched alkyl group, an aryl group, —COR ′ (where R ′ is a hydrogen atom, a linear or A branched alkyl group, a cycloalkyl group, an adamantyl group, or an aryl group, which may have a substituent and may be condensed with a substituted or unsubstituted benzene ring) or —CO ₂ R ″ (where R ″ is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an adamantyl group, or an aryl group, which may have a substituent, and may be substituted or unsubstituted. Which may be condensed with a benzene ring), and these may have a substituent.

In the present specification, the “cycloalkyl group” refers to a C _3-8 cycloalkyl group which may contain a hetero atom, such as cyclopentyl, cyclohexyl, cycloheptyl and the like. As used herein, “heteroatom” refers to 1 to 4 heteroatoms selected from, for example, nitrogen, sulfur and oxygen.
In the present specification, the “substituted or unsubstituted benzene ring” refers to a benzene ring substituted with 0 to 5 substituents.

  Examples of “—COR ′” include acetyl group, perfluoroacetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, mesitylcarbonyl group and the like, and “—COOR” ”includes methoxycarbonyl group, Examples thereof include, but are not limited to, ethoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, cyclooctyloxycarbonyl group, benzyloxycarbonyl group, ethyloxycarbonyl group, cyclohexyloxycarbonyl group, adamantyloxycarbonyl group, and the like. It is not a thing.

Specific examples of the optically active cobalt (II) complex include those represented by the following formula.

  The optically active cobalt (II) complex represented by this general formula can be prepared according to a known method (for example, Y. Nishida, et al, Inorg. Chim. Acta, 38, 213 (1980), EG Jager, Z. Chem., 8, 30, 392, and 475 (1968)). For example, it can be prepared by a method in which a ligand corresponding to the complex and an aqueous sodium hydroxide solution are heated in methanol in a nitrogen atmosphere and then an aqueous cobalt (II) chloride solution is added.

  The “catalytic amount” of the optically active cobalt (II) complex catalyst used in the present invention is 0.1 to 50 mol%, preferably 1 to 10 mol%, relative to 1 mol of the racemic secondary alcohol.

  In the present invention, it is necessary for the catalyst to coexist with an olefin. The “olefin” used in the present invention refers to an unsaturated hydrocarbon having one or more carbon double bonds, such as ethylene, propylene, 1-butene, 3,3-dimethyl-1-butene, isobutene, 2- Ethyl-1-butene, 2-methyl-1-pentene, 2,3,3-trimethyl-1-butene, styrene, especially styrene substituted with electron withdrawing groups such as o-, m-, p-fluorostyrene O-, m-, p-chlorostyrene, o-, m-, p-bromostyrene, o-, m-, p-methoxystyrene, o-, m-, p-trifluoromethylstyrene, o-, m-, p-methylstyrene, etc. are mentioned. Particularly preferred are styrene and p-chlorostyrene. Here, the “electron-withdrawing group” refers to a group that easily attracts electrons from the bonding atom side as compared with a hydrogen atom, and is not particularly limited, and is preferably a halogen atom, particularly preferably chlorine.

  The amount of the olefin used in the present invention can be appropriately changed, for example, 10 to 150 mol%, preferably 20 to 120 mol%, more preferably 40 to 80 mol% with respect to 1 mol of the secondary alcohol. Is the ratio. In order to obtain an optically active secondary alcohol with high optical yield and high chemical yield, it is preferably 50 to 80 mol%, preferably 60 to 70 mol% with respect to 1 mol of the secondary alcohol. is there.

で表され、Ｒ⁶およびＲ⁷は異なる有機基であり、ここで該有機基は互いに結合してもよい。 In the method of the present invention, the racemic secondary alcohol has the formula:

R ⁶ and R ⁷ are different organic groups, wherein the organic groups may be bonded to each other.

  In the present specification, the “organic group” refers to a group having a carbon atom as a basic skeleton, for example, a linear or branched alkyl group, a linear or branched alkenyl group, or an aryl group, which are substituted. It may have a group.

In the present specification, the “linear or branched alkenyl group” means, for example, vinyl group, allyl group, isopropenyl group, 2-methylallyl group, 1-propenyl group, 2-methyl-1-propenyl group, 1-butenyl. A C _1-12 linear or branched alkenyl group such as a group, 2-butenyl group, and 3-butenyl group;
Alternatively, R ⁶ and R ⁷ are bonded to each other to form a cycloalkyl group, which may contain a hetero atom, may have a substituent, and contains a spiro carbon to form a spiro ring. It may be condensed with a substituted or unsubstituted benzene ring.

When the cycloalkyl group forms a spiro ring, it forms a new C _3-7 cycloalkane ring with the spiro carbon, such as 4′-hydroxy-spiro [cyclohexane-1,2′-chroman], 4 '-Hydroxy-spiro [cyclopentane-1,2'-chroman] and the like.

Specific examples of the racemic secondary alcohol include those represented by the following formula.

The pressure of the “oxygen molecule” used in the present invention is not particularly limited, but is 0.1 MPa to 10 MPa, preferably 0.2 MPa to 5 MPa, more preferably 0.2 MPa to 2 MPa. The oxygen molecules used in the present invention may be used in the form of a mixed gas. For example, air can be used instead of pure oxygen.
Examples of the solvent used in the present invention include aromatic hydrocarbons and alcohols such as t-butyl alcohol, t-amyl alcohol, m-xylene, mesitylene, 1,2,3,4-tetramethylbenzene, 1, 2,3,5-tetramethylbenzene, 2-methylnaphthalene, toluene, n-propylbenzene, n-hexylbenzene, cyclohexylbenzene, t-butylbenzene, etc. are mentioned, preferably t-butyl alcohol, t-amyl alcohol , T-butylbenzene.
The reaction temperature is usually from 0 ° C to 90 ° C, particularly preferably from room temperature to 50 ° C. Here, “room temperature” means a temperature of 15 ° C. to 30 ° C.
The reaction time varies depending on the reaction scale, reaction conditions, such as the amount of styrene.

製造に用いられる水およびメタノールは予め脱気した。メタノール（２ｍｌ）中のＮ,Ｎ’−ビス［２−エトキシカルボニル−３−オキソブチリデン）−（１Ｓ,２Ｓ）−ジメシチルエチレンジアミン（０.３７ｍｍｏｌ）透明溶液に、６０℃で、Ｎ₂下、トリエチルアミン（０.１１ｍｌ、０.７７ｍｍｏｌ）を添加した。１０分間撹拌した後、メタノール（１ｍｌ）中の塩化コバルト（II）（７３ｍｇ、０.５５ｍｍｏｌ）を滴下した。次いで、水（０.５ｍｌ）を添加し、橙色固体を沈殿させた。室温に冷まし、液相をＮ₂下で濾別し、得られた橙色固体を水（０.５ｍｌ）で洗浄した。分析的に純粋なコバルト(II)錯体を、油浴で真空乾燥した後、橙色粉末として得た。73％収率 ; Mp 218 ℃ (DSC); MS (FAB⁺) m/z 633 (M⁺). Production Example 1
[N, N′-bis (2-ethoxycarbonyl-3-oxobutylidene)-(1S, 2S) -dimesitylethylenediaminato] cobalt (II):

Water and methanol used for production were degassed in advance. To a clear solution of N, N′-bis [2-ethoxycarbonyl-3-oxobutylidene)-(1S, 2S) -dimesitylethylenediamine (0.37 mmol) in methanol (2 ml) at 60 ° C. under N ₂ , Triethylamine (0.11 ml, 0.77 mmol) was added. After stirring for 10 minutes, cobalt (II) chloride (73 mg, 0.55 mmol) in methanol (1 ml) was added dropwise. Water (0.5 ml) was then added and an orange solid precipitated. Cooled to room temperature, the liquid phase was filtered off under N ₂ and the resulting orange solid was washed with water (0.5 ml). Analytical pure cobalt (II) complex was obtained as an orange powder after vacuum drying in an oil bath. 73% yield; Mp 218 ° C (DSC); MS (FAB ⁺ ) m / z 633 (M ⁺ ).

製造例１と同様の方法により、表題化合物を得た。74％収率 ; Mp 250 ℃ (DSC); MS (FAB⁺) m/z 741 (M⁺). Production Example 2
[N, N′-bis (2-cyclohexyloxycarbonyl-3-oxobutylidene)-(1S, 2S) -dimesitylethylenediaminato] cobalt (II):

The title compound was obtained in the same manner as in Production Example 1. 74% yield; Mp 250 ° C (DSC); MS (FAB ⁺ ) m / z 741 (M ⁺ ).

製造例１と同様の方法により、表題化合物を得た。75％収率 ; Mp 334 ℃ (DSC); MS (FAB⁺) m/z 845 (M⁺). Production Example 3
[N, N′-bis (2- (2-adamantyl) oxycarbonyl-3-oxobutylidene)-(1S, 2S) -dimesitylethylenediaminato] cobalt (II):

The title compound was obtained in the same manner as in Production Example 1. 75% yield; Mp 334 ° C (DSC); MS (FAB ⁺ ) m / z 845 (M ⁺ ).

Example 1
Cobalt (II) complex obtained from Preparation Example 2 (18.54 mg, 0.025 mmol) and 1,2,3,4-tetrahydro-1-naphthol (37.05 mg, in t-BuOH (1.5 mL) To a solution of 0.25 mmol) styrene (18.6 ml, 0.65 eq) was added under O ₂ at room temperature and the solution was stirred at 50 ° C. for 12 hours. The reaction was quenched by the addition of saturated aqueous sodium thiosulfate and the product was extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium sulfate. The solvent was evaporated in vacuo and purified by column chromatography on silica gel (hexane / ethyl acetate, 8: 1) and the corresponding alcohol (16.6 mg, 45% yield, 91% ee, k _rel value) as a colorless oil. 21) was obtained.

Examples 2-18
The reactions of Examples 2 to 18 were carried out in the same manner as described in Example 1, except that the cobalt (II) complex (0.025 mmol) obtained from Preparation Example 2 in t-BuOH (1.5 mL), the substrate (0.25 mmol) and styrene (0.65 eq) were used at 50 ° C. under O ₂ .
However, in Examples 2, 7, 8, 11, 13, and 15, the catalyst used was the cobalt (II) complex obtained from Production Example 3, and Examples 2, 3, 4, 6, 7, 8, 14, In 15, 17, and 18, p-chlorostyrene was used instead of styrene, and in Examples 8, 9, 10 and 11, the solvent was t-butylbenzene and the reaction temperature was 65 ° C.

ここで「ｅｅ」とは、エナンチオマー過剰率（ｅｎａｎｔｉｏｍｅｒｉｃ ｅｘｃｅｓs）を表し、これは試料中に占めるＲ体とＳ体の割合をそれぞれＲおよびＳとすると、次式：
ｅｅ（％）＝｛(Ｒ−Ｓ）/(Ｒ＋Ｓ）または(Ｓ−Ｒ）/(Ｒ＋Ｓ）｝×１００
で求められる。
また、「ｋ_rel」とは、ラセミ体第２級アルコールの各光学異性体の反応速度比を表し、以下により示される：

本発明において、ｋ_relは１０以上、好ましくは１５以上、特に好ましくは２０以上である。 The results of the examples are shown in the table below.

Here, “ee” represents an enantiomeric excess, which is represented by the following formula when the ratio of R-form and S-form in the sample is R and S, respectively:
ee (%) = {(R−S) / (R + S) or (S−R) / (R + S)} × 100
Is required.
“K _rel ” represents the reaction rate ratio of each optical isomer of the racemic secondary alcohol, and is represented by the following:

In the present invention, k _rel is 10 or more, preferably 15 or more, particularly preferably 20 or more.

  ADVANTAGE OF THE INVENTION According to this invention, the optically active secondary alcohol useful as a raw material compound of a medical agrochemical product and a functional raw material compound can be provided with high optical purity, and also the quantity of the olefin to be used is adjusted. Since the conversion rate of the reaction can be easily and arbitrarily controlled, the industrial value is very high.

Claims (6)

formula:

(Wherein R ⁶ and R ⁷ are each a linear or branched alkyl group, a linear or branched alkenyl group or an aryl group, which are substituted or unsubstituted, or
R ⁶ and R ⁷ are bonded to each other to form a cycloalkyl group, which may contain a hetero atom, may be substituted or unsubstituted, and may contain a spiro carbon to form a spiro ring. , May be condensed with a substituted or unsubstituted benzene ring,
Here, the substituent that can be substituted is an alkyl group, an alkoxy group, or a halogen atom), and a racemic secondary alcohol represented by the formula:

[Wherein, R ¹ and R ² are different groups, each of which is a hydrogen atom, a linear or branched alkyl group, or an aryl group, which are substituted or unsubstituted,
Two R ^{1 s} or two R ^{2 s} may be bonded to each other to form a ring,
R ³ , R ⁴ and R ⁵ may be the same or different and are a hydrogen atom, a linear or branched alkyl group, an aryl group, or —COR ′ (where R ′ is a hydrogen atom, linear or branched). of
An alkyl group, a cycloalkyl group, an adamantyl group, or an aryl group, which are substituted or unsubstituted and optionally fused with a substituted or unsubstituted benzene ring) or —CO ₂ R ″ (where R "Is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an adamantyl group, or an aryl group, which are substituted or unsubstituted, and may be condensed with a substituted or unsubstituted benzene ring. These are substituted or unsubstituted,
Here, the substituent that can be substituted is an alkyl group, an alkoxy group, or a halogen atom]
In the presence of a catalytic amount of an optically active cobalt (II) complex catalyst represented by the formula, an olefin that is styrene or p-chlorostyrene is allowed to coexist in a solvent, so that only one optical isomer of the racemate is selected. A method for producing an optically active secondary alcohol, characterized in that the other optical isomer of a racemate is recovered as an unreacted secondary alcohol by being oxidized with an oxygen molecule and converted into a corresponding ketone. One of R ¹ and R ² is hydrogen, the other is an aryl group, and R ³ , R ⁴ and R ⁵ may be the same or different, and may be a hydrogen atom, linear or branched alkyl A group, —COR ′ (where R ′ is a linear or branched alkyl group or aryl group) or —CO ₂ R ″ (where R ″ is a linear or branched alkyl group, cycloalkyl group or The production method according to claim 1 , which is an adamantyl group. One of R ¹ and R ² is hydrogen, the other is a mesityl group, R ³ is a hydrogen atom, R ⁴ and R ⁵ may be the same or different, and methyl, acetyl, mesi The production method according to claim 2 , which is tilcarbonyl, ethoxycarbonyl, cyclohexyloxycarbonyl, or (2-adamantyl) oxycarbonyl. The optically active cobalt (II) complex catalyst is [N, N′-bis (2-ethoxycarbonyl-3-oxobutylidene)-(1S, 2S) -dimesitylethylenediaminato] cobalt (II), [N, N '-Bis (2-cyclohexyloxycarbonyl-3-oxobutylidene)-(1S, 2S) -dimesitylethylenediaminato] cobalt (II), and [N, N′-bis (2- (2-adamantyl) oxy The process according to claim 3 , wherein the process is selected from carbonyl-3-oxobutylidene)-(1S, 2S) -dimesitylethylenediaminato] cobalt (II). Olefin is a good styrene substituted with an electron withdrawing group, The process according to claim 1-4. Either one of R ⁶ and R ⁷ is an aryl group and the other is a linear or branched alkyl group, or R ⁶ and R ⁷ are bonded to each other to form a cycloalkyl group; This is condensed with a substituted or unsubstituted benzene ring, wherein the substituents which may be substituted, an alkyl group, an alkoxy group, a halogen atom, a process according to claims 1-5.