JPH11209387A - Optically active manganese complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new complex comprising a specific optically active manganese complex, capable of catalyzing an optically active epoxidizing reaction of various olefins in high asymmetric yield and useful for the production, etc., of medicines, agrochemicals, perfumes, cosmetics, natural physiologically active compounds, etc. SOLUTION: This new optically active manganese complex is represented by formula I [R<1> and R<2> are each a 1-8C alkyl, a 3-7C cycloalkyl, a 7-11C aralkyl or a 6-10C aryl; R<3> is a 1-8C alkyl, a 3-7C cycloalkyl, a 7-11C aralkyl, a 6-10C aryl; OH, COOH, a 2-8C alkyloxycarbonyl, a 7-11C aryloxycarbonyl, a di-1-8C alkyloxyboronoxy or the like; (n) is 0 or 1; X is a halide ion, a 2-8C carboxylate ion or PF6 ) and is useful as a catalyst, etc., for an optically active epoxidizing reaction, etc. of olefins. The complex is obtained by reacting a hydroxyaldehyde derivative represented by formula II with a manganese salt and an optically active 1,1'-bi-naphthyl-2,2'-diamine derivative represented by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an optically active manganese complex, and more particularly to an optically active manganese complex and a method for producing an optically active epoxide compound from an olefin using the optically active manganese complex.

[0002]

2. Description of the Related Art Several asymmetric epoxidation reactions of olefins have been known. For example, there is a Katsuki-shrapless reaction using a tartrate ester and titanium tetraisopropoxide as asymmetric sources (T. Kats
uki, K .; B. Sharpless, J .; Am. Ch
em. Soc. , 102, 5974 (1980)). However, this reaction was effective only for the olefin portion of the aryl alcohol, and could not be used for other olefins. In recent years, highly enantioselective catalytic asymmetric epoxidation of simple olefins without special functional groups has been studied, and Katsuki et al. And Jacobsen et al. Have developed optically active salen-type manganese complexes. High selectivity has been obtained for high simple olefins (R. Irie, K. Noda, Y. Ito, N. et al.
Matsumoto, and T.M. Katsuki, T
etrahedron Lett. , 31,7345
(1990); Zhang, J .; L. Loebac
h, S. R. Wilson, and E.W. N. Jaco
bsen, J .; Am. Chem. Soc. , 112,2
801 (1990)). Also, Narita and Maruyama et al. Have found that an optically active iron porphyrin complex is effective for a substrate mainly composed of styrene (Y. Narut).
a, F. Tani, N .; Ishihara, and K .;
Maruyama, J .; Am. Chem. Soc. , 1
13, 6865 (1991)). Several other methods are known. Among these, the only effective reaction for a wide range of simple olefins is the reaction using an optically active salen-type manganese complex by Katsuki et al. And Jacobsen et al. However, these complexes generally have high enantioselectivity with respect to cis-type olefins, but do not have sufficient enantioselectivity with respect to trans-type olefins at present.

[0003]

An object of the present invention is to develop an optically active manganese complex having a high enantioselectivity not only for cis-type olefins but also for trans-type olefins for simple olefins having no special functional groups. Another object of the present invention is to efficiently produce various optically active epoxide compounds by a catalytic reaction.

[0004]

The present inventors have conducted intensive studies to find an optically active manganese complex that can satisfy high enantioselectivity for cis- and trans-type simple olefins having no special functional groups. Epoxidation using an optically active manganese complex [I] and an oxidizing agent (sodium hypochlorite or iodosylbenzene) in an amount of 95 to 100% for not only cis-olefins but also trans-olefins. An epoxide compound having a high optical purity of ee was successfully obtained in a high chemical yield. Furthermore, as a result of intensive research to find an optically active manganese complex that can satisfy high enantioselectivity for olefins having a functional group such as a halogen group, a carbonyl group, a hydroxyl group, an ether substituent, a nitrile group, a nitro group, and a nitroso group, When a Lewis acid group such as boron is introduced into the molecule, an epoxide compound having a similar extremely high optical purity was successfully obtained in a high chemical yield, thereby completing the present invention.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In this specification, n is normal, i is iso, sec is secondary, t or tert is tertiary, Me is methyl, Et is ethyl, Bu is butyl, P
h represents phenyl, and THF represents tetrahydrofuran.

The compound of the present invention will be specifically described.
Examples of the substituent of R ^{1 in} the formula [I] include the following. The C ₁ -C ₈ alkyl group includes a linear or branched saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms (hereinafter, the alkyl group has the same meaning), Such alkyl groups include methyl, ethyl, n
-Propyl, i-propyl, n-butyl, i-butyl,
sec-butyl, tert-butyl, n-pentyl, n
-Hexyl, n-heptyl and n-octyl groups.

A C ₃ -C ₇ cycloalkyl group is a cyclic saturated aliphatic hydrocarbon group having 3 to 7 carbon atoms (hereinafter referred to as “C ₃ -C ₇ cycloalkyl group”).
Cycloalkyl groups have the same meaning), and such cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups.

The C ₇ -C ₁₁ aralkyl group includes an araliphatic hydrocarbon group having 7 to 11 carbon atoms (hereinafter, the aralkyl group has the same meaning). Benzyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, o-
Chlorobenzyl, m-chlorobenzyl, p-chlorobenzyl, phenethyl, o-methylphenethyl, m-methylphenethyl, p-methylphenethyl, 3-phenylpropyl, 3- (o-methylphenyl) propyl, 3- (m
-Methylphenyl) propyl, 3- (p-methylphenyl) propyl, 4-phenylbutyl, α-naphthylmethyl and β-naphthylmethyl groups.

The C ₆ -C ₁₀ allyl group includes an aromatic hydrocarbon group having 6 to 10 carbon atoms (hereinafter, the allyl group has the same meaning). Phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3 , 5-dimethylphenyl, 2,3,4-trimethylphenyl, 2,
3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 3,4,5-trimethylphenyl, 3,4
6-trimethylphenyl, 2,4,6-trimethylphenyl, α-naphthyl and β-naphthyl groups.

The following are examples of the substituent of R ² . Examples of the C ₁ -C ₈ alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl and and n-octyl group.

Examples of the C ₃ -C ₇ cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.

As the C ₇ -C ₁₁ aralkyl group, benzyl, o-methylbenzyl, m-methylbenzyl, p-
Methylbenzyl, o-chlorobenzyl, m-chlorobenzyl, p-chlorobenzyl, phenethyl, o-methylphenethyl, m-methylphenethyl, p-methylphenethyl, 3-phenylpropyl, 3- (o-methylphenyl) propyl, 3- (m-methylphenyl) propyl,
3- (p-methylphenyl) propyl, 4-phenylbutyl, α-naphthylmethyl and β-naphthylmethyl groups.

The C ₆ -C ₁₀ allyl group includes phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-
Dimethylphenyl, 2,6-dimethylphenyl, 3, 4
-Dimethylphenyl, 3,5-dimethylphenyl, 2,
3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 3,4
5-trimethylphenyl, 3,4,6-trimethylphenyl, 2,4,6-trimethylphenyl, α-naphthyl and β-naphthyl groups.

The substituents of R ³ include the following. Examples of the C ₁ -C ₈ alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl and and n-octyl group.

Examples of the C ₃ -C ₇ cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups.

As the C ₇ -C ₁₁ aralkyl group, benzyl, o-methylbenzyl, m-methylbenzyl, p-
Methylbenzyl, o-chlorobenzyl, m-chlorobenzyl, p-chlorobenzyl, phenethyl, o-methylphenethyl, m-methylphenethyl, p-methylphenethyl, 3-phenylpropyl, 3- (o-methylphenyl) propyl, 3- (m-methylphenyl) propyl,
3- (p-methylphenyl) propyl, 4-phenylbutyl, α-naphthylmethyl and β-naphthylmethyl groups.

The C ₆ -C ₁₀ allyl group includes phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-
Dimethylphenyl, 2,6-dimethylphenyl, 3, 4
-Dimethylphenyl, 3,5-dimethylphenyl, 2,
3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 3,4
5-trimethylphenyl, 3,4,6-trimethylphenyl, 2,4,6-trimethylphenyl, α-naphthyl and β-naphthyl groups.

Examples include a hydroxyl group and a carboxyl group.

The C ₂ -C ₈ alkyloxycarbonyl group includes methyloxycarbonyl, ethyloxycarbonyl, n-propyloxycarbonyl, i-propyloxycarbonyl, n-butyloxycarbonyl, i-butyloxy Examples thereof include a carbonyl group, a sec-butyloxycarbonyl group, a tert-butyloxycarbonyl group, an n-pentyloxycarbonyl group, an n-hexyloxycarbonyl group, and an n-heptyloxycarbonyl group.

The C ₇ -C ₁₁ allyloxycarbonyl group includes a phenyloxycarbonyl group, a 2-tolyloxycarbonyl group, a 3-tolyloxycarbonyl group,
Tolyloxycarbonyl group, 2-ethylphenyloxycarbonyl group, 3-ethylphenyloxycarbonyl group, 4-ethylphenyloxycarbonyl group, 2,3-
Dimethylphenyloxycarbonyl group, 2,4-dimethylphenyloxycarbonyl group, 2,5-dimethylphenyloxycarbonyl group, 2,6-dimethylphenyloxycarbonyl group, 2-n-propylphenyloxycarbonyl group, 3-n- Propylphenyloxycarbonyl group, 4-n-propylphenyloxycarbonyl group,
2-i-propylphenyloxycarbonyl group, 3-i
-Propylphenyloxycarbonyl group, 4-i-propylphenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group and the like.

Examples of the di-C ₁ -C ₈ alkyloxyboronoxy group include a dimethyloxyboronoxy group, a diethyloxyboronoxy group, a di-n-propyloxyboronoxy group, a di-i-propyloxyboronoxy group, a di-n-
Butyloxyboronoxy group, dii-butyloxyboronoxy group, disec-butyloxyboronoxy group,
Di-tert-butyloxyboronoxy group, di-n-pentyloxyboronoxy group, di-n-hexyloxyboronoxy group, di-n-heptyloxyboronoxy group, di-n-octyloxyboronoxy group, 1,2-ethane Examples include a dioxyboronoxy group and a 1,3-propanedioxyboronoxy group.

Examples of the di-C ₃ -C ₇ cycloalkyloxyboronoxy group include dicyclopropyloxyboronoxy group, dicyclobutyloxyboronoxy group, dicyclopentyloxyboronoxy group, dicyclohexyloxyboronoxy group, and dicycloheptyl. An oxyboronoxy group;

Examples of the di-C ₇ -C ₁₁ aralkyloxyboronoxy group include a dibenzyloxyboronoxy group, a di-2-phenylethyloxyboronoxy group, a di-3-phenyln-propyloxyboronoxy group, and a di-4-phenyl. n-butyloxyboronoxy group, di1,1-dimethyl-2-phenylethyloxyboronoxy group, di1-
And a naphthylmethyloxyboronoxy group, a di-2-naphthylmethyloxyboronoxy group and the like.

The di C ₆ -C ₁₀ allyloxyboronoxy group includes a diphenyloxyboronoxy group and a di-2-
Tolyloxyboronoxy, di-3-tolyloxyboronoxy, di-4-tolyloxyboronoxy, di2
-Ethylphenyloxyboronoxy group, di-3-ethylphenyloxyboronoxy group, di-4-ethylphenyloxyboronoxy group, di2,3-dimethylphenyloxyboronoxy group, di2,4-dimethylphenyloxyboronoxy group Group, di 2,5-dimethylphenyloxyboronoxy group, di 2,6-dimethylphenyloxyboronoxy group, di-2-n-propylphenyloxyboronoxy group, di-3-n-propylphenyloxyboronoxy group, Di-4-n-propylphenyloxyboronoxy group, di-2-i-propylphenyloxyboronoxy group, di3-i-propylphenyloxyboronoxy group, di-4-i-propylphenyloxyboronoxy group, di2 -N-butylphenyloxyboronoxy group,
Di-3-n-butylphenyloxyboronoxy group, di4
-N-butylphenyloxyboronoxy group, di-2-i
-Butylphenyloxyboronoxy group, di-3-i-butylphenyloxyboronoxy group, di4-i-butylphenyloxyboronoxy group, di2-sec-butylphenyloxyboronoxy group, di-3-sec-butyl Phenyloxyboronoxy group, di4-sec-butylphenyloxyboronoxy group, di-2-tert-butylphenyloxyboronoxy group, di-3-tert-butylphenyloxyboronoxy group, di-4-tert-
Examples thereof include a butylphenyloxyboronoxy group, a di-1-naphthyloxyboronoxy group, and a di-2-naphthyloxyboronoxy group.

The C ₆ -C ₁₀ allyldioxyboronoxy group includes catecholboronoxy group, naphthalene 1,2-dioxyboronoxy group, naphthalene 2,3-
And a dioxyboronoxy group and a naphthalene 1,8-dioxyboronoxy group.

Examples of X ^- include the following.
Examples of the halide ion include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.

As the C ₂ -C ₈ carboxylate ion,
Acetate ion, propionate ion, n-butyrate ion, isobutyrate ion, cyclopropanecarboxylate ion, n
-Valerate, isovalerate, pivalate,
2-methylbutyrate, cyclobutanecarboxylate, n-hexanoate, isohexanoate, cyclopentanecarboxylate, n-heptanoate, isoheptanoate, cyclohexanecarboxylate, benzoate, 2-methylbenzoate Acid ion,
Examples include 3-methylbenzoate ion, 4-methylbenzoate ion, n-octanoate ion, isooctanoate ion, and cycloheptanecarboxylate ion.

[0028] PF ₆ ^- can be mentioned.

As the compound of the present invention represented by the formula [I], the compounds shown in Tables 1 to 3 can be exemplified, but the present invention is not limited to these compounds. In Tables 1 to 3, the symbol "M
"e" represents a methyl group, "Et" represents an ethyl group, "i-Pr" represents an isopropyl group, "t-Bu" represents a tertiary butyl group, and "Ph" represents a phenyl group.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

Next, the method for synthesizing the optically active manganese complex [I] and the asymmetric epoxidation reaction of an asymmetric olefin compound using the same will be described in detail.

The optically active manganese complex [I] provided by the present invention can be prepared by a known method [Katsuki et al.
e, K .; Noda, Y .; Ito, N .; Matsusumo
o, and T. Katsuki, Tetrahedr
on Lett. , 31, 7345 (1990)), J.
acobsen et al. (W. Zhang, JLL).
oebach, S .; R. Wilson, andE.
N. Jacobsen, J. et al. Am. Chem. So
c. , 112, 2801 (1990))].
It can be easily produced in a high yield in one or two steps.

The following reaction formula shows the synthesis route of the optically active manganese complex represented by the formula [I]. In the formula, R ¹ , R ² , R ³ , n, and X represent the same meaning as described above.

[0036]

Embedded image

In this reaction, the hydroxyaldehyde compound [I
V], a manganese salt [V] and an optically active 1,1′-binaphthyl-2,2′-diamine [VI] reaction to synthesize an optically active manganese complex [I]. Salicylaldehyde, 3
-Ethyl salicylaldehyde, 3,5-dimethyl salicylaldehyde, 4,6-di-tert-butyl salicylaldehyde, 3-ethyl-5-i-propyl salicylaldehyde, 5-benzyl-3-ethyl salicylaldehyde,
-T-butyl-6-phenylsalicylaldehyde, 4-
t-butyl-3-ethylsalicylaldehyde, 5-benzyl-4-t-butylsalicylaldehyde, 3-ethyl-4-carboxysalicylaldehyde, 4-t-butyl-5-methoxycarbonylsalicylaldehyde, 4-hydroxysalicylaldehyde , 4-catecholboronoxysalicylaldehyde, 6-methoxyboronoxysalicylaldehyde, 3-ethyl-2-hydroxyphenylacetaldehyde, 3,5-dimethyl-2-hydroxyphenylacetaldehyde, 4,6-di-t-butyl-
2-hydroxyphenylacetaldehyde, 3-ethyl-2-hydroxy-5-i-propylphenylacetaldehyde, 5-benzyl-3-ethyl-2-hydroxyphenylacetaldehyde, 4-t-butyl-2-hydroxy-6-phenylacetaldehyde 4-t-butyl-3-ethyl-2-hydroxyphenylacetaldehyde, 5-benzyl-4-t-butyl-2-hydroxyphenylacetaldehyde, 3-ethyl-4-carboxy-2-hydroxyphenylacetaldehyde, 4-t
-Butyl-2-hydroxy-5-methoxycarbonylphenylacetaldehyde, 2,4-dihydroxyphenylacetaldehyde, 4-catecholboronoxy-2
-Hydroxyphenylacetaldehyde, 6-methoxyboronoxy-2-hydroxyphenylacetaldehyde and the like can be used. Preferably, salicylaldehyde, 3,5-dimethyl salicylaldehyde, 4,6
-Di-tert-butyl salicylaldehyde, 4-hydroxysalicylaldehyde, 4-catecholboronoxysalicylaldehyde, 3,5-dimethyl-2-hydroxyphenylacetaldehyde, 4,6-di-tert-butyl-2-hydroxyphenylacetaldehyde, -T-butyl-
2-hydroxy-5-methoxycarbonylphenylacetaldehyde, 2,4-dihydroxyphenylacetaldehyde, 4-catecholboronoxy-2-hydroxyphenylacetaldehyde and the like. More preferably, salicylaldehyde, 4,6-di-t-butylsalicylaldehyde, 4-hydroxysalicylaldehyde,
-Catecholboronoxysalicylaldehyde, 4,6
-Di-tert-butyl-2-hydroxyphenylacetaldehyde, 2,4-dihydroxyphenylacetaldehyde, 4-catecholboronoxy-2-hydroxyphenylacetaldehyde and the like. Examples of the manganese salt [V] include manganese (II) acetate, manganese (II) propionate, manganese (II) benzoate, manganese (II) fluoride, manganese (II) chloride, and manganese (II) bromide.
I), manganese (II) iodide and the like can be used. Preferred are manganese (II) acetate and manganese (II) chloride. The optically active 1,1′-binaphthyl-2,2′-diamine [VI] includes (R)-
1,1′-binaphthyl-2,2′-diamine, (S)
-1,1′-binaphthyl-2,2′-diamine,
(R) -1,1′-binaphthyl-3,3′-dimethyl-2,2′-diamine, (S) -1,1′-binaphthyl-3,3′-dimethyl-2,2′-diamine, (R)
-1,1'-binaphthyl-7,7'-dimethyl-2,
2'-diamine, (S) -1,1'-binaphthyl-
7,7'-dimethyl-2,2'-diamine, (R)-
1,1'-binaphthyl-8,8'-dimethyl-2,2
'-Diamine, (S) -1,1'-binaphthyl-8,
8'-dimethyl-2,2'-diamine, (R) -1,1
'-Binaphthyl-3,3'-diphenyl-2,2'-
Diamine, (S) -1,1'-binaphthyl-3,3 '
-Diphenyl-2,2'-diamine, (R) -1,1 '
-Binaphthyl-7,7'-diphenyl-2,2'-diamine, (S) -1,1'-binaphthyl-7,7'-
Diphenyl-2,2'-diamine, (R) -1,1'-
Binaphthyl-8,8'-diphenyl-2,2'-diamine, (S) -1,1'-binaphthyl-8,8'-diphenyl-2,2'-diamine and the like can be used. Preferably, (R) -1,1′-binaphthyl-
2,2′-diamine, (S) -1,1′-binaphthyl-2,2′-diamine, (R) -1,1′-binaphthyl-8,8′-dimethyl-2,2′-diamine, (S)
-1,1'-binaphthyl-8,8'-dimethyl-2,
2'-diamine, (R) -1,1'-binaphthyl-
8,8'-diphenyl-2,2'-diamine, (S)-
1,1'-binaphthyl-8,8'-diphenyl-2,
2′-diamine and the like. More preferably, (R)-
1,1′-binaphthyl-2,2′-diamine, (S)
-1,1′-binaphthyl-2,2′-diamine,
(R) -1,1'-binaphthyl-8,8'-dimethyl-2,2'-diamine and (S) -1,1'-binaphthyl-8,8'-dimethyl-2,2'-diamine is there.
The reaction solvent used in this reaction is an alcoholic solvent such as acetonitrile, methanol, ethanol, n-propanol, i-propanol, diethyl ether, di-n-propyl ether, tetrahydrofuran, 1,3
Ether solvents such as-and 1,4-dioxane can be used. Preferred are acetonitrile, ethanol and tetrahydrofuran. More preferred are acetonitrile and ethanol. The reaction temperature is from -78 to
It can be carried out at a temperature up to 50 ° C., preferably −1
It is good to carry out in the range of 0 to 20 ° C.

On the other hand, the optically active manganese complex [I]
It is stable to light, water, and heat, and has good solubility in various solvents. In addition, the optically active manganese complex [I] may be an organic solvent or an organic solvent-water 2 depending on the type of the oxidizing agent.
It can be used in both layer systems.

Using the optically active manganese complex [I] thus obtained, an asymmetric olefin compound [II]
Can be stereoselectively epoxidized to obtain corresponding optically active epoxide compounds [III].

[0040]

Embedded image

The substituents of the compounds represented by the formulas [II] and [III] are described below.

At least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is a substituent different from the others, and is a hydrogen atom, C ₁ -C ₈
Alkyl group, C ₃ -C ₇ cycloalkyl group, C ₇ -C
₁₁ aralkyl group, C ₆ -C ₁₀ allyl group, halogen (F, Cl, Br, I) substituted C ₁ -C ₈ alkyl, halogen (F, Cl, Br, I) substituted C ₃ -C ₇ cycloalkyl , Halogen (F, Cl, Br, I) substituted C ₇
-C ₁₁ aralkyl group, halogen (F, Cl, Br,
I) substituted _C 6 _{-C 10} aryl _group, C 1 -C ₈ alcohol _group, C 3 _{-C 10} allyl alcohol _group, C 6 _{-C 10}
Phenolic hydroxyl group, C ₁ -C ₈ carboxylic acid group, C _1-
C ₈ ester _groups, C 1 -C ₈ amide _group, C 1 _{-C 10} acyl _group, C 1 -C ₈ ether _{substituents,} C 1 -C ₈ nitroalkyl _group, C 1 -C ₈ nitroso alkyl group, _{C 1} -C
_{8 represents a} cyanoalkyl group. In addition, R ⁴ and R ⁵ , R ⁴
And R ⁶ , R ⁴ and R ⁷ may take a ring structure integrally.

As the C ₁ -C ₈ alkyl group, methyl,
Ethyl, n-propyl, i-propyl, n-butyl, i
-Butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-hexyl and the like.

Examples of the C ₃ -C ₇ cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.

As the C ₇ -C ₁₁ aralkyl group, benzyl, o-methylbenzyl, m-methylbenzyl, p-
Methylbenzyl, phenethyl, o-methylphenethyl,
Examples thereof include m-methylphenethyl, p-methylphenethyl, phenylpropyl, o-methylphenylpropyl, m-methylphenylpropyl, p-methylphenylpropyl, phenylbutyl, α-naphthylmethyl, and β-naphthylmethyl group.

As the C ₆ -C ₁₀ allyl group, phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-
Dimethylphenyl, 2,6-dimethylphenyl, 3, 4
-Dimethylphenyl, 3,5-dimethylphenyl, 2,
3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 3,4
5-trimethylphenyl, 3,4,6-trimethylphenyl, 2,4,6-trimethylphenyl, α-naphthyl, β-naphthyl and the like.

Halogen (F, Cl, Br, I) substituted C
The ₁ -C ₈ alkyl group, fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, dichloromethyl, dibromomethyl, diiodomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, 2-fluoroethyl, 2
-Chloroethyl, 2-bromoethyl, 2-iodoethyl, 3-fluoropropyl, 3-chloropropyl, 3-
Bromopropyl, 3-iodopropyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, 4-iodobutyl, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl, 7-fluoroheptyl, 7
-Chloroheptyl, 7-bromoheptyl, 7-iodoheptyl, 8-fluorooctyl, 8-chlorooctyl,
8-bromooctyl, 8-iodooctyl group and the like.

Halogen (F, Cl, Br, I) substituted C
The ₃ -C ₇ cycloalkyl group, 2-fluoro-cyclopropyl, 2-chloro-cyclopropyl, 2-bromo-cyclopropyl, 2-iodo-cyclopropyl, 3-fluoro-cyclobutyl, 3-chloro-cyclobutyl, 3- Buromoshikuro Butyl, 3-iodocyclobutyl, 3-fluorocyclopentyl, 3-chlorocyclopentyl, 3-bromocyclopentyl, 3-iodocyclopentyl, 4-fluorocyclohexyl, 4-chlorocyclohexyl,
-Bromocyclohexyl, 4-iodocyclohexyl,
4-fluorocycloheptyl, 4-chlorocycloheptyl, 4-bromocycloheptyl, 4-iodocycloheptyl and the like.

Halogen (F, Cl, Br, I) substituted C
The ₆ -C ₁₀ aryl group, 2-fluorophenyl,
2-chlorophenyl, 2-bromophenyl, 2-iodophenyl, 3-fluorophenyl, 3-chlorophenyl, 3-bromophenyl, 3-iodophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodo Phenyl, 2-fluorobenzyl, 2
-Chlorobenzyl, 2-bromobenzyl, 2-iodobenzyl, 3-fluorobenzyl, 3-chlorobenzyl,
3-bromobenzyl, 3-iodobenzyl, 4-fluorobenzyl, 4-chlorobenzyl, 4-bromobenzyl, 4-iodobenzyl, 3-fluoro-2,6-dimethylphenyl, 3-chloro-2,6-dimethyl Phenyl, 3-bromo-2,6-dimethylphenyl, 3-iodo-2,6-dimethylphenyl, 4-fluoro-2,6
-Dimethylphenyl, 4-chloro-2,6-dimethylphenyl, 4-bromo-2,6-dimethylphenyl, 4-
Iodo-2,6-dimethylphenyl, 3-fluoro-
2,4,6-trimethylphenyl, 3-chloro-2,
4,6-trimethylphenyl, 3-bromo-2,4,6
-Trimethylphenyl, 3-iodo-2,4,6-trimethylphenyl, 1-fluoro-2-naphthyl, 1-fluoro-3-naphthyl, 1-fluoro-4-naphthyl,
1-fluoro-5-naphthyl, 1-fluoro-6-naphthyl, 1-fluoro-7-naphthyl, 1-fluoro-8
-Naphthyl, 1-chloro-2-naphthyl, 1-chloro-
3-naphthyl, 1-chloro-4-naphthyl, 1-chloro-5-naphthyl, 1-chloro-6-naphthyl, 1-chloro-7-naphthyl, 1-chloro-8-naphthyl, 1-bromo-2- Naphthyl, 1-bromo-3-naphthyl, 1-
Bromo-4-naphthyl, 1-bromo-5-naphthyl, 1
-Bromo-6-naphthyl, 1-bromo-7-naphthyl,
1-bromo-8-naphthyl, 1-iodo-2-naphthyl, 1-iodo-3-naphthyl, 1-iodo-4-naphthyl, 1-iodo-5-naphthyl, 1-iodo-6-naphthyl, 1- Iodo-7-naphthyl, 1-iodo-8-
Naphthyl, 2-fluoro-1-naphthyl, 2-fluoro-3-naphthyl, 2-fluoro-4-naphthyl, 2-fluoro-5-naphthyl, 2-fluoro-6-naphthyl,
2-fluoro-7-naphthyl, 2-fluoro-8-naphthyl, 2-chloro-1-naphthyl, 2-chloro-3-naphthyl, 2-chloro-4-naphthyl, 2-chloro-5-
Naphthyl, 2-chloro-6-naphthyl, 2-chloro-7
-Naphthyl, 2-chloro-8-naphthyl, 2-bromo-
1-naphthyl, 2-bromo-3-naphthyl, 2-bromo-4-naphthyl, 2-bromo-5-naphthyl, 2-bromo-6-naphthyl, 2-bromo-7-naphthyl, 2-bromo-8- Naphthyl, 2-iodo-1-naphthyl, 2-
Iodo-3-naphthyl, 2-iodo-4-naphthyl, 2
-Iodo-5-naphthyl, 2-iodo-6-naphthyl,
2-iodo-7-naphthyl, 2-iodo-8-naphthyl group, and the like.

Examples of the C ₁ -C ₈ alcohol group include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, and 8-hydroxyoctyl. And the like.

Examples of the C ₃ -C ₁₀ allyl alcohol group include 3-hydroxypropenyl, 3-hydroxybutenyl, 3-hydroxypentenyl, 5-hydroxy-3-
Pentenyl, 3-hydroxyhexenyl, 6-hydroxy-4-hexenyl, 2-hydroxymethylphenyl,
3-hydroxymethylphenyl, 4-hydroxymethylphenyl, 2-hydroxymethyl-3-methylphenyl, 2-hydroxymethyl-4-methylphenyl, 3-
Hydroxymethyl-4-methylphenyl, 4-hydroxymethyl-2-methylphenyl, 2- (2-hydroxyethyl) phenyl, 3- (2-hydroxyethyl) phenyl, 4- (2-hydroxyethyl) phenyl, 2-
(3-hydroxypropyl) phenyl, 3- (3-hydroxypropyl) phenyl, 4- (3-hydroxypropyl) phenyl, 2- (4-hydroxybutyl) phenyl, 3- (4-hydroxybutyl) phenyl, 4- (4
-Hydroxybutyl) phenyl group.

Examples of the C ₆ -C ₁₀ phenolic hydroxyl group include 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-hydroxy-3-methylphenyl, 2-hydroxy-4-methylphenyl,
2-hydroxy-5-methylphenyl, 2-hydroxy-6-methylphenyl, 3-hydroxy-2-methylphenyl, 3-hydroxy-4-methylphenyl, 3-hydroxy-5-methylphenyl, 3-hydroxy-6 −
Methylphenyl, 4-hydroxy-2-methylphenyl, 4-hydroxy-3-methylphenyl, 2-hydroxy-3-ethylphenyl, 2-hydroxy-4-ethylphenyl, 2-hydroxy-5-ethylphenyl,
-Hydroxy-6-ethylphenyl, 3-hydroxy-
2-ethylphenyl, 3-hydroxy-4-ethylphenyl, 3-hydroxy-5-ethylphenyl, 3-hydroxy-6-ethylphenyl, 4-hydroxy-2-ethylphenyl, 4-hydroxy-3-ethylphenyl,
2-hydroxy-3-propylphenyl, 2-hydroxy-4-propylphenyl, 2-hydroxy-5-propylphenyl, 2-hydroxy-6-propylphenyl, 3-hydroxy-2-propylphenyl, 3-hydroxy-4 -Propylphenyl, 3-hydroxy-5-
Propylphenyl, 3-hydroxy-6-propylphenyl, 4-hydroxy-2-propylphenyl, 4-hydroxy-3-propylphenyl, 1-hydroxy-2
-Naphthyl, 1-hydroxy-3-naphthyl, 1-hydroxy-4-naphthyl, 1-hydroxy-5-naphthyl, 1-hydroxy-6-naphthyl, 1-hydroxy-
7-naphthyl, 1-hydroxy-8-naphthyl, 2-hydroxy-1-naphthyl, 2-hydroxy-3-naphthyl, 2-hydroxy-4-naphthyl, 2-hydroxy-
5-naphthyl, 2-hydroxy-6-naphthyl, 2-hydroxy-7-naphthyl, 2-hydroxy-8-naphthyl group, and the like.

The C ₁ -C ₈ carboxylic acid group includes carboxyl, carboxylmethyl, carboxylethyl, carboxylpropyl, carboxylbutyl, carboxylpentyl, carboxyhexyl, 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl, carboxyphenyl Heptyl, 2-carboxy-4-methylphenyl, 3-carboxy-4-methylphenyl, 4-
And a carboxy-2-methylphenyl group.

As the C ₂ -C ₈ ester group, methyl ester, ethyl ester, n-propyl ester, i-
Examples include propyl ester, n-butyl ester, i-butyl ester, sec-butyl ester, tert-butyl ester, n-pentyl ester, n-hexyl ester, phenyl ester, and n-heptyl ester groups.

As the C ₁ -C ₈ amide group, carbamoyl, carbamoylmethyl, 2-carbamoylethyl, 3
Carbamoylpropyl, 4-carbamoylbutyl, 5
-Carbamoylpentyl, 6-carbamoylhexyl,
2-carbamoylphenyl, 3-carbamoylphenyl, 4-carbamoylphenyl, 7-carbamoylheptyl, 2-carbamoyl-4-methylphenyl, 3-carbamoyl-2-methylphenyl, 4-carbamoyl-
And a 2-methylphenyl group.

The C ₁ -C ₁₀ acyl group includes formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, benzoyl, 2-methylbenzoyl, 3-methylbenzoyl,
-Methylbenzoyl, 2-ethylbenzoyl, 3-ethylbenzoyl, 4-ethylbenzoyl, 2-n-propylbenzoyl, 3-n-propylbenzoyl, 4-n-
A propylbenzoyl, 1-naphthoyl, 2-naphthoyl group and the like.

C ₁ -C ₈ ether substituents include methoxy, methoxymethyl, methoxyethyl, methoxy n-
Propyl, methoxy n-butyl, methoxy n-pentyl, methoxy n-hexyl, 2-methoxyphenyl,
-Methoxyphenyl, 4-methoxyphenyl, methoxy n-heptyl, 2-methoxy-4-methylphenyl,
-Methoxy-2-methylphenyl group and the like.

The C ₁ -C ₈ nitroalkyl groups include nitromethyl, nitroethyl, nitro n-propyl, nitro n-butyl, nitro n-pentyl, nitro n-hexyl, 2-nitrophenyl, 3-nitrophenyl, −
Nitrophenyl, nitro n-heptyl, 2-nitro-4
-Methylphenyl, 3-nitro-2-methylphenyl,
4-nitro-2-methylphenyl group and the like.

The C ₁ -C ₈ nitrosoalkyl group includes
Nitrosomethyl, Nitrosoethyl, Nitroso n-propyl, Nitroso n-butyl, Nitroso n-pentyl, Nitroso n-hexyl, 2-Nitrophenyl, 3-Nitrosocyphenyl, 4-Nitrosophenyl, Nitroso n-heptyl, 2-Nitroso -4-methylphenyl, 3-nitroso-2-methylphenyl, 4-nitroso-2-methylphenyl group and the like.

The C ₁ -C ₈ cyanoalkyl group includes cyanomethyl, cyanoethyl, cyano n-propyl, cyano n-butyl, cyano n-pentyl, cyano n-hexyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, Cyanophenyl, cyano n-heptyl, 2-cyano-4-
Methylphenyl, 3-cyano-2-methylphenyl, 4
-Cyano-2-methylphenyl group and the like.

Examples of the cyclic structure in which R ⁴ and R ⁵ are integrated include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, and cyclodecanilidene. Reden and the like.

The cyclic structure in which R ⁴ and R ⁶ are integrated includes 1-methylcyclopropene, 1-methylcyclobutene, 1-methylcyclopentene, 1-methylcyclohexene, 1-ethylcyclopropene, 1-ethylcyclo Butene, 1-ethylcyclopentene, 1-ethylcyclohexene, 1-n-propylcyclopropene, 1-n-
Propylcyclobutene, 1-n-propylcyclopentene, 1-n-propylcyclohexene, 1-i-propylcyclopropene, 1-i-propylcyclobutene, 1
-I-propylcyclopentene, 1-i-propylcyclohexene, 1-n-butylcyclopropene, 1-n-
Butylcyclobutene, 1-n-butylcyclopentene,
1-n-butylcyclohexene, 1-i-butylcyclopropene, 1-i-butylcyclobutene, 1-i-butylcyclopentene, 1-i-butylcyclohexene,
-Sec-butylcyclopropene, 1-sec-butylcyclobutene, 1-sec-butylcyclopentene, 1
-Sec-butylcyclohexene, 1-sec-butylcyclopropene, 1-sec-butylcyclobutene, 1
-Sec-butylcyclopentene, 1-sec-butylcyclohexene, 1-tert-butylcyclopropene, 1-tert-butylcyclobutene, 1-tert
-Butylcyclopentene, 1-tert-butylcyclohexene, 1-tert-butylcyclopropene, 1-
Examples include tert-butylcyclobutene, 1-tert-butylcyclopentene, 1-tert-butylcyclohexene, and the like.

Examples of the cyclic structure in which R ⁴ and R ⁷ are integrated include trans-cyclooctene, trans-cyclononene, trans-cyclodeken, E-1-methylcyclooctene, E-1-methylcyclononene, E-1
-Methylcyclodeken and the like.

The reaction solvent for this reaction is diethyl ether, di-n-propyl ether, tetrahydrofuran,
Ether solvents such as 1,3- or 1,4-dioxane,
Halogen solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride; hydrocarbon solvents such as pentane, hexane and benzene; nitrile solvents such as acetonitrile; water-halogen solvents (dichloromethane, dichloroethane, chloroform, carbon tetrachloride, etc.) )) Can be used. Preferably, dichloromethane,
Halogen solvents such as dichloroethane, chloroform and carbon tetrachloride, two-layer solvents such as water-halogen solvents (dichloromethane, dichloroethane, chloroform and carbon tetrachloride), and nitrile solvents such as acetonitrile are preferably used. More preferably, water-dichloromethane, dichloromethane, and acetonitrile are used. The reaction temperature is
It can be carried out in the range of -100 ° C to 80 ° C, preferably in the range of -78 ° C to 40 ° C, and more preferably in the range of -10 ° C to 30 ° C.

When this reaction is performed stoichiometrically, the optically active manganese complex [I] is used in an equimolar amount to the asymmetric olefin [II]. On the other hand, when this reaction is carried out catalytically, the optically active manganese complex [I] is added to the asymmetric olefin [II] by 1/10 to 1/1000.
It can be used in a molar ratio of 0. In this case, the amount of the oxidizing agent is 1 to 1 with respect to the asymmetric olefin [II].
It can be used in a molar ratio of 50 times.

[0066]

The asymmetric olefin represented by the formula [II] is epoxidized with a simple operation using the optically active manganese complex represented by the formula [I], thereby obtaining a high asymmetric yield and a high chemical yield. Thus, the desired optically active epoxide compound represented by the formula [III] could be synthesized. In addition, the compound of the present invention has a high asymmetric yield and a high chemical activity with respect to the optically active 1,2-diol structure, β-amino alcohol structure and epoxide structure of pharmaceuticals, agricultural chemicals, flavors, cosmetics, natural physiologically active compounds and the like. It is possible to synthesize in a yield.

[0067]

EXAMPLES Example 1 Synthesis of Optically Active Manganese Complex [I] Manganese (III)-(R) or (S) -1,1′-binaphthyl-2,2 ′-(2-oxidephenyl) imine -Acetate Complex [I-1] Synthesis

[0068]

Embedded image

Salicylaldehyde 244 mg (2 m
mol) was dissolved in 10 ml of ethanol, and 245 mg (1 mmol) of manganese (II) acetate tetrahydrate was added thereto to give 2
Stirred for 0 minutes. 284 mg of (R) or (S) -1,1′-binaphthyl-2,2′-diamine (1 mmo
l) was added and stirred for 5 hours. The precipitated yellow-brown crystals were collected by filtration, and manganese (III)-(R) or (S) -1,1
'-Binaphthyl-2,2'-(2-oxidephenyl) imine-acetate complex [I-1] (600 mg,
Yield 99%). (Example 2) Synthesis of optically active manganese complex [I] Manganese (III)-(R) or (S) -1,1'-binaphthyl-2,2- (4-hydroxy-2-oxidephenyl) imine- Synthesis of acetate complex [I-2]

[0070]

Embedded image

2,4-dihydroxybenzaldehyde 2
76 mg (2 mmol) was dissolved in 10 ml of ethanol, and 245 mg (1 ml) of manganese (II) acetate tetrahydrate was dissolved.
mol) and stirred for 20 minutes. (R) or (S)-
1,1'-binaphthyl-2,2'-diamine 284m
g (1 mmol) was added and the mixture was stirred for 5 hours. The precipitated yellow-brown crystals were collected by filtration, and manganese (III)-(R) or (S) -1,1′-binaphthyl-2,2 ′-(4-hydroxy-2-oxidephenyl) imine-acetate complex [ I-2] (490 mg, yield 77%) was obtained. Example 3 Synthesis of Optically Active Manganese Complex [I] Manganese (m)-(R) or (S) -1,1′-binaphthyl-2,2 ′-(4-catecholboronoxy-2)
-Oxidephenyl) imine-acetate complex [I-
Synthesis of 3]

[0072]

Embedded image

Manganese (III)-(R) or (S)-
1,1'-binaphthyl-2,2 '-(4-hydroxy-2-oxidephenyl) imine-acetate complex [I
-2] 159 mg (0.25 mmol) in dry THF
Dissolve in 2 ml and stir with 1M catechol borane.
THF complex THF solution 0.5 ml (0.5 mmol)
Was gradually added while paying attention to the generation of hydrogen gas. After stirring for 3 hours, the solvent was distilled off under reduced pressure, and the residue was washed with a small amount of ethanol to remove manganese (III)-(R) or (S) -1,1'-binaphthyl-2,2 '-( 4-Catecholboronoxy-2-oxidephenyl) imine-acetate complex [I-3] (218 mg, yield 100
%).

Optically active manganese (III) -1,1'-
Binaphthyl-2,2 '-(2-oxidephenyl) imine-acetate complex [I-1], optically active manganese (III) -1,1'-binaphthyl-2,2'-(4
-Hydroxy-2-oxidephenyl) imine-acetate complex [I-2] and optically active manganese (III)-
Catalytic asymmetric epoxidation of unsymmetric olefin [II] with 1,1'-binaphthyl-2,2 '-(4-catecholboronoxy-2-oxidephenyl) imine-acetate complex [I-3] (Method A ) 29.8m of 11% sodium hypochlorite aqueous solution
1 (44 mmol) disodium hydrogen phosphate 568
mg (4 mmol) to dissolve and stir,
A 1M aqueous solution of sodium hydroxide (suitable amount) was added, and pH 1
Adjusted to 1.3. Next, the optically active manganese complex [I-
1 or I-2 or I-3] 0.01 mmol and 1 mmol of asymmetric olefin were dissolved in 3 ml of dichloromethane. The aqueous sodium hypochlorite solution was ice-cooled, a dichloromethane solution was added, and the mixture was stirred for 20 hours. The reaction solution was diluted with 200 ml of dichloromethane, washed with water, and dried over anhydrous magnesium sulfate. After filtering off anhydrous magnesium sulfate, dichloromethane was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to quantitatively obtain the desired optically active epoxide compound [III]. (Method B) Optically active manganese complex [I-1 or I-2 or I-3] 0.01 mmol and asymmetric olefin 1 m
was dissolved in 10 ml of acetonitrile, 1.1 g (5 mmol) of iodosylbenzene was added, and the mixture was stirred at room temperature for 8 hours. After the reaction solution was distilled off under reduced pressure, the residue was extracted with 50 ml of dichloromethane, washed with water and dried over anhydrous magnesium sulfate. After filtering off anhydrous magnesium sulfate, dichloromethane was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to quantitatively obtain the desired optically active epoxide compound [III].

Table 4 shows the optically active manganese (III) -1,
1'-binaphthyl-2,2 '-(2-oxidephenyl) imine-acetate complex [I-1], optically active manganese (III) -1,1'-binaphthyl-2,2'-
(4-hydroxy-2-oxidephenyl) imine-acetate complex [I-2] and optically active manganese (II)
I) -1,1'-Binaphthyl-2,2 '-(4-catecholboronoxy-2-oxidephenyl) imine-
The results of catalytic asymmetric epoxidation of various asymmetric olefins using the acetate complex [I-3] are shown. The asymmetric yield and absolute configuration of the obtained epoxide compound were compared with those of the optically active sample compound by high performance liquid chromatography analysis and gas chromatography analysis using a chiral column, and ¹ H-NM using a chiral shift reagent.
Determined by R spectrum analysis.

[0076]

[Table 4]

Various cis- and trans-type simple olefins using the compounds [I-1], [I-2] and [I-3] of the present invention or asymmetric epoxy compounds of olefins having a halogen group or a carbonyl group In the reaction, a high asymmetric yield was obtained with a 1 / 100-fold molar amount of the catalyst. For this reason, practical application can be strongly expected. To date, little is known about the effective reactions for both cis and trans simple olefins. In addition, olefins having various functional groups also have high enantioselectivity with the same amount of catalyst, so that their generality is further expanded, and they are extremely superior to conventional technologies.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07M 7:00

Claims (2)

[Claims] (1) Formula (I): (Wherein, R ¹ is a C ₁ -C ₈ alkyl group, a C ₃ -C ₇ cycloalkyl group, a C ₇ -C ₁₁ aralkyl group or a C ₆ -C 7
Shows the ₁₀ allyl group, ^{R 2} represents a _C 1 -C ₈ alkyl _group, C 3 -C ₇ cycloalkyl _group, C 7 _{-C 11} aralkyl or _C 6 _{-C 10} aryl group, ^{R 3} is _{C 1} - C ₈ alkyl group, C ₃ -C ₇ cycloalkyl group, C ₇ -C ₁₁ aralkyl group or C ₆ -C ₁₀ allyl group, hydroxyl group, carboxyl group, C ₂ -C ₈ alkyloxycarbonyl group, C ₇ -C ₁₁ Allyloxycarbonyl group, di-C ₁ -C ₈ alkyloxyboronoxy group, di-C ₃ -C ₇ cycloalkyloxyboronoxy group, di-C
₇ -C ₁₁ aralkyloxy boron group, di _{C 6} -
C ₁₀ allyloxy boron oxy group, a C ₆ -C ₁₀ aryl dioxy boron group, such as catechol boron group and naphthalene dioxy boron group, n represents an integer of 0 or 1, X ^- A, halide _ions, carboxylate ions C 2 -C _8, PF ₆ ^- are shown. An optically active manganese complex represented by). 2. A compound of the formula [II]: (In the formula, at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is a substituent different from the others, and is a hydrogen atom, a C ₁ -C ₈ alkyl group, a C ₃ -C ₇ cycloalkyl group, a C ₇ -C ₁₁ aralkyl group, C ₆ -C ₁₀ allyl group, halogen-substituted C
₁ -C ₈ alkyl group, a halogen-substituted _C 3 -C ₇ cycloalkyl group, _C 7 _{-C 11} aralkyl group halogen-substituted, _C 6 _{-C 10} aryl group a halogen _substituted, C 1 -C ₈
Alcohol _group, C 3 _{-C 10} allyl alcohol group, _{C 6}
-C ₁₀ phenolic hydroxyl _groups, C 1 -C ₈ carboxylic _acid, C 2 -C ₈ ester _groups, C 1 -C ₈ amide group, _{C 1}
—C ₁₀ acyl group, C ₁ -C ₈ ether substituent, C ₁ —
A C ₈ nitroalkyl group, a C ₁ -C ₈ nitrosoalkyl group, or a C ₁ -C ₈ cyanoalkyl group;
R ⁴ and R ⁵ , R ⁴ and R ⁶ , R ⁴ and R ⁷ may be taken together to form a cyclic structure), and an asymmetric olefin represented by the formula [I] according to claim 1. Epoxidation with an active manganese complex yields formula [III]: (Wherein, R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meaning as described above, and * indicates an optically active center). Production of active epoxide compounds.