JPS6156225B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for asymmetrically synthesizing optically active aziridines. More specifically, sulfuimines having optical activity on the sulfur atom are reacted with olefins such as α/β-unsaturated ketones or α/β-unsaturated carboxylic acid esters, resulting in asymmetric synthesis in one step. This is a method for asymmetric synthesis of aziridines. Until now, it has not been known that optically active aziridines can be obtained either by optical resolution or by asymmetric synthesis. Because optically active aziridines are optically active, they can be expected to have excellent effects in various fields, particularly as pharmaceuticals and pharmaceutical synthesis intermediates, and a general and easy synthesis method has been desired. The present inventors studied Michael-type addition reactions between olefins substituted with electron-withdrawing groups and sulfyl imines, and found that, for example, olefins substituted with electron-withdrawing groups with strong resonance effects such as carbonyl groups and carboxylic acid ester groups. They discovered that only the corresponding trans-aziridines can be obtained by using either the cis or trans isomer, and have already applied for a patent. The present inventors have further conducted intensive research on the addition reaction between olefins such as α/β-unsaturated ketones or α/β-unsaturated carboxylic acid esters and sulfilimines having optical activity on the sulfur atom.
The present invention was completed based on the discovery that the optical activity on the sulfur atom can be asymmetrically induced into aziridine and optically active trans-aziridines can be obtained in a one-step reaction. That is, the present invention is based on the formula (In the formula, R ¹ and R ² represent an alkyl group, an aryl group, an alkyl-substituted aryl group, and an alkoxy-substituted aryl group, and R ³ represents hydrogen, an alkyl group, a cycloalkyl group, and an aralkyl group.) Optically active sulfylimines () having optical activity on the atom and the formula (In the formula, R ⁴ , R ⁵ , and R ⁶ represent hydrogen, an aryl group, an alkoxycarbonyl group, and an arylcarbonyl group, and R ⁷ represents an alkyl group, an aryl group, an alkyl-substituted aryl group, an alkoxy-substituted aryl group, and a halogen-substituted aryl group. group, alkoxy group.However, R ⁴ and R ⁵ are not the same. (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same as above.) This is an asymmetric synthesis method for optically active aziridines (). In the addition reaction of sulfuimine to olefins such as α/β-unsaturated ketones or α/β-unsaturated carboxylic esters, α/β-unsaturated ketones or α/β-unsaturated carboxylic esters, etc. It has already become clear through research by the present inventors that regardless of whether the cis or trans form of the olefins is used, only the corresponding trans-aziridines can be specifically obtained. When considering the configuration of aziridines, there is no optically active form in the cis form, and only two types of optically active forms, (2R, 3S) and (2S, 3R), exist in the trans form. In the asymmetric synthesis method of the present invention, for example, when the R form of sulfuimine is reacted with an olefin such as an α/β-unsaturated ketone or an α/β-unsaturated carboxylic acid ester, the corresponding (2R, The optically active trans-aziridines of 3S) were obtained in good optical yield, and the S form of sulfuimine and α/β-
When unsaturated ketones or olefins such as α/β-unsaturated carboxylic acid esters are reacted, corresponding (2S, 3R) optically active trans-aziridines can be obtained in good optical yield. This is because the sulfoylimino group first undergoes a Michael-type addition reaction to the β-position carbon atom of olefins such as α/β-unsaturated ketones or α/β-unsaturated carboxylic acid esters, and at that time, the sulfuilimine sulfur Optical activity on the atom is β of olefin
This is thought to be due to the asymmetric induction onto the carbon atom in the position, and then, due to reasons such as steric crowding, it adopts a dominant steric configuration, that is, a trans-configuration, and cyclizes. In the present invention, the sulfyl imine () having optical activity on the sulfur atom includes N-unsubstituted, N-unsubstituted, N-
-Any substituted sulfuilimine may be used, N-
As the N-substituent of the substituted sulfuilimine, an electron-donating group is preferable since the addition reaction of the present invention is a nucleophilic addition reaction. Examples of R ¹ and R ² in sulfoylimines () having optical activity on the sulfur atom include methyl group, ethyl group, propyl group, butyl group,
Saturated alkyl groups such as tert-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, vinyl group, 1-propenyl group, 4-hexenyl group, 9-
Unsaturated alkyl groups such as pentadecenyl group, cycloalkyl group such as cyclopropyl group, cyclohexyl group, unsaturated cycloalkyl group such as cyclohexenyl group, aryl group such as phenyl group, tolyl group, naphthyl group, benzyl group, phenethyl group Examples include hydrocarbon groups such as aralkyl groups such as R ¹ and R ²
may form a ring, and examples of the sulfur-containing cyclic compound include thiolane, thian, oxathian, 1.
Examples thereof include 2-dihydrothionaphthene, benzothiane, thiabicycloheptane, phenoxatin, phenothiazi, thioxanthene, and the like. Examples of R ³ include hydrogen, methyl group, ethyl group, propyl group, butyl group, tert-butyl group, hexyl group,
Saturated alkyl groups such as 2-ethylhexyl group and dodecyl group; unsaturated alkyl groups such as vinyl group, 1-propenyl group, 4-hexenyl group, and 9-pentadecenyl group; cycloalkyl group such as cyclopropyl group and cyclohexyl group; Unsaturated cycloalkyl groups such as hexenyl groups, phenyl groups, tolyl groups,
Examples include hydrocarbon groups such as aryl groups such as naphthyl groups and aralkyl groups such as phenethyl groups. Substituents that can be substituted on the hydrocarbon groups of R ¹ , R ² and R ³ are not particularly limited, but include, for example, halogen, alkoxy group, aryloxy group, alkylthio group, arylthio group, nitro group, acyl group, Examples include a sulfonyl group and a cyano group. Examples of the optically active sulfuimines () of the present invention include S-phenyl-S-o-tolylsulfylimine, S-phenyl-S-o-methoxyphenylsulfylimine, S-p-tolyl-S- o-chlorophenylsulfuimine, S
-p-Bromo-S-o-chlorophenylsulfuimine, S-phenyl-S-m-chlorophenylsulfuimine, S-phenyl-S-2.4
-dichlorophenylsulfuimine, S-p-
Methylthiophenyl-S-phenylsulfuimine, S-phenyl-S-3,4-dimethoxyphenylsulfuimine, S-methyl-S-phenylsulfuimine, S-ethyl-S-p-tolyl Sulfuilimine, S-cyclopropyl-S
-Phenylsulfuilimine, S-propyl-S
-o-acetylphenylsulfuimine, S-
Cyclohexyl-S-p-chlorophenylsulfuilimine, S-ethyl-S-cyclohexylsulfuimine, S-methyl-S-decylsulfuimine, S-methyl-S-cyclopropylsulfuimine, S-ethyl- S-hexylsulfyl imine, S-vinyl-S-phenylsulfyl imine, S-vinyl-S-hexyl sulfyl imine, S-phenyl-S-benzyl sulfyl imine, S-methyl-S-benzyl sulfyl imine N- having optical activity on the sulfur atom such as imine, etc.
Unsubstituted sulfyl imines, N-methyl-S-phenyl-S-o-tolylsulfyl imine, N-
Ethyl-S-phenyl-S-o-bromophenylsulfuimine, N-cyclopropyl-S-methyl-S-phenylsulfuimine, N-hexyl-S-methyl-S-p-tosylphenylsulf Filmimine, N-octyl-S-methyl-S-
Ethylsulfuilimine, N-cyclopropyl-
S-propyl-S-phenylsulfuimine,
N-phenyl-S-phenyl-S-p-nitrophenylsulfuimine, N-p-chlorophenyl-S-methyl-S-cyclohexylsulfuimine, N-o-methoxyphenyl-S-methyl-S- o-ethylthiophenylsulfuimine, N-benzyl-S-phenyl-S-o-cyanophenylsulfuimine, N-methylimino-2-methylthiolane, N-phenylimino-2
-Methoxythian, N-vinyl-S-phenyl-
S-o-methoxyphenylsulfuimine, N
-Methyl-S-methyl-S-naphthylsulfuilimine, N-methyliminobenzothiazole, and other N-substituted sulfuilimines. The olefins such as α/β-unsaturated ketones or α/β-unsaturated carboxylic acid esters of the present invention are:
An olefin derivative substituted with at least one electron-withdrawing group having a strong resonance effect such as a carbonyl group or a carboxylic acid ester group,
R ⁴ , R ⁵ , and R ⁶ may be an electron-withdrawing group or an electron-donating group, and there is no particular limitation, but R ⁴
and R ⁵ must not be the same. Examples of R ⁴ and R ⁵ in the olefins () include hydrogen, methyl group, ethyl group, propyl group, butyl group, tert-butyl group, hexyl group,
Saturated alkyl groups such as 2-ethylhexyl group and dodecyl group; unsaturated alkyl groups such as vinyl group, 1-propenyl group, 4-hexenyl group, and 9-pentadecenyl group; cycloalkyl group such as cyclopropyl group and cyclohexyl group; Unsaturated cycloalkyl groups such as hexenyl groups, phenyl groups, tolyl groups,
Aryl groups such as naphthyl groups, aralkyl groups such as benzyl groups and phenethyl groups, heterocyclic carbon groups such as furyl groups, furfuryl groups, thienyl groups, pyrrolyl groups, pyridyl groups, morifolinyl groups, imidazolyl groups, and tetrahydrofuranyl groups. hydrocarbon groups such as, carbonyl groups, carboxylic acid ester groups, ethers, thioethers and sulfonyls, fluorine, chlorine, bromine, substituted with the hydrocarbon groups described as R ⁴ and R ⁵ of olefins (), Indicates halogen such as iodine. R ⁷ represents the above hydrocarbon group described as R ⁴ and R ⁵ of olefins () and -OA, and A represents the above hydrocarbon group described as R ⁴ and R ⁵ of olefins (). show. There are no particular restrictions on the substituents that can be substituted on the hydrocarbon group, carbonyl group, carboxylic acid ester group, ether, thioether, sulfonyl group, etc. of R ⁴ , R ⁵ , R ⁶ , R ⁷ , but for example,
Examples include halogen, alkoxy group, aryloxy group, alkylthio group, arylthio group, nitro group, acyl group, sulfonyl group, and cyano group. Examples of the olefins () of the present invention include 1-acetyl-2-methylethylene, 1-benzoyl-2-propylethylene, 1-lauroyl-2-phenylethylene, 1-acetyl-2-
Methyl-2-propylethylene, 1-acetyl-
2-benzylethylene, 1-tolylcarbonyl-
1-Methyl-2-phenylethylene, 1-phenylacetyl-2-phenylethylene, 1-butyroyl-2-chloroethylene, 1-benzoyl-
1,2-dichloroethylene, 1-acetyl-2-
Bromoethylene, 1-benzoyl-2-methoxyethylene, 1-acetyl-2-methylthioethylene, 1-isobutyryl-2-phenylsulfonylethylene, 1-benzoyl-2-cyanoethylene, 1,2-dibenzoylethylene, 1・2-dibenzoyl-1-methylethylene, 1-acetyl-1-benzoyl-2-methylethylene, 1-benzoyl-2-methoxycarbonylethylene, 1
-benzoyl-1-methoxycarbonyl-2-t
-butylethylene, 1,2-dibenzoyl-1-
Chloroethylene, 1,2-diacetylethylene,
1,1-dibenzoyl-2-methylethylene, 1
-acetyl-2-cyclohexylethylene, 1-
Benzoyl-2-allylethylene, 1-butyryl-2-furifurylethylene, 1-cyclohexylcarbonyl-2-phenylethylene, 1-benzoyl-2-thianylethylene, 1-acetyl-2
-morpholinylethylene, 1-(2,4-dichlorophenylcarbonyl)-2-methylethylene,
1-benzoyl-2-(4-methoxyphenyl)
Ethylene, 1-(4-nitrophenylcarbonyl)-2-acetylethylene, 1-(4-tosylphenylcarbonyl)-2-methylethylene, 1-
α/β-unsaturated ketones such as benzoyl-2-(2-methylthiophenyl)ethylene, methyl crotonate, phenyl 2-propylacrylate, hexyl 2-phenylcrotonate, 2-benzyl acrylic acid methyl ester, 2-propylisocrotonic acid benzyl ester, 2-tolyl methacrylic acid propyl ester,
2-cyclohexyl acrylic acid ethyl ester,
2-allyl acrylic acid methyl ester, 2-piperidyl acrylic acid hexyl ester, 2-pyrazolyl methacrylic acid t-butyl ester, 1-thioranyl crotonate isopropyl ester, 2-thienyl crotonate 2-ethylhexyl ester,
2-chloroacrylic acid ethyl ester, 1,2-
Dichloroacrylic acid benzyl ester, 2-bromo-1-ethyl acrylic acid phenyl ester, 1
-Phenyl-2-methoxyacrylic acid isobutyl ester, 2-ethylthio-2-phenyl acrylic acid methyl ester, 2-tosyl acrylic acid cyclohexyl ester, 2-cyano-1-propylcarboxylic acid neopentyl ester, fumaric acid diisopropyl ester, Dioctyl maleate, methyl 1,2-dichlorofumarate, dicyclohexyl 1-ethylmaleate, diethyl 1-bromomaleate,
1-Methoxycarbonylcrotonic acid t-butyl ester, 1-propoxycarbonyl-2-chloroacrylic acid 2-ethylhexyl ester, fumaric acid diallyl ester, crotonic acid allyl ester, 1-(2-chlorophenyl)2-ethyl acrylic acid methyl ester , 2-(2,4-dichlorophenyl)crotonic acid 2-ethylhexyl ester, fumaric acid di(2-methoxyethyl) ester, 2-(4-bromophenyl)-acrylic acid neopentyl ester, 1-(4-methoxy phenyl)maleic acid diisopropyl ester, 2-
(2-Nitrophenyl)methacrylic acid 2-chloroethyl ester, 2-(2-tosylethyl)methacrylic acid octyl ester, 2-(3-methylthiopropyl)acrylic acid allyl ester, 1-
(4-acetylphenyl)-2-phenylacrylic acid (2-ethylthioethyl) ester, 2-(2
-bromoethyl)crotonic acid cyclohexyl ester, fumaric acid di(2-tosylethyl) ester, and other α/β-unsaturated carboxylic acid esters.Whether these olefins are in the trans or cis form, included. The present invention can be easily implemented, for example, as follows. For example, sulfuimine, which has optical activity on the sulfur atom, α/β-unsaturated ketone, and α/β-
Mix olefins such as unsaturated carboxylic acid esters in theoretical amounts, use a solvent if necessary,
The reaction is usually carried out at room temperature, with heating or cooling if necessary. The reaction is usually completed in several minutes to several hours, but heating for a long time is optional if necessary. After the reaction, column chromatography,
Optically active aziridines are obtained by separation by conventional means such as gas chromatography, recrystallization, and distillation. If necessary, the optical purity can be further increased by purification operations such as recrystallization. Sulfyl imines having optical activity on the sulfur atom are, for example, asymmetric synthesis method by reacting an asymmetric sulfide, an optically active alcohol, a halogenating agent with an amide anion or an aryl amine, or a racemic sulfyl imine obtained by a conventional method. It can be easily obtained by inoculating seeds of optically active sulfuimine onto sulfur atoms and optically resolving them. In the present invention, as the solvent used if necessary, ordinary solvents are preferably used, such as saturated hydrocarbons such as hexane and octane, aromatic hydrocarbons such as benzene, toluene, and xylene,
Alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol; ethers such as diethyl ether, tetrahydrofuran, anisole, and ethylene glycol diethyl ether; ketones such as acetone, methyl isobutyl ketone, and acetylacetone; and esters such as ethyl acetoacetate and ethyl acetate. Nitriles such as acetonitrile and isobutyronitrile; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and trichloroethylene; nitrogen-containing compounds such as dimethylformamide; and sulfur-containing compounds such as dimethyl sulfoxide. These solvents may be used alone or in combination. Optically active aziridines are extremely useful compounds as pharmaceuticals and pharmaceutical synthesis intermediates, and the present invention has made their synthesis possible for the first time. The asymmetric synthesis method for optically active aziridines of the present invention allows optically active aziridines with good optical purity to be obtained in good yield in a one-step reaction, and raw materials are easily available.
This is an extremely excellent method that can be implemented industrially. As described above, the present invention greatly contributes to this industry by providing aziridines with high optical purity in a one-step reaction. Examples will be described below. Example 1 230 mg of trans-1-benzoyl-2-phenylethylene and 346 mg ([α] _D = +
164.5°, optical purity 84.8%) and methylene chloride 0.5
ml, mix and stir at 50°C for 48 hours. The reaction solution was separated by column chromatography (filling material: silica gel, developing solvent: CHCl ₃ ), and (-)-trans-2-benzoyl-3-phenylaziridine was separated.
184 mg (yield 66%, [α] _D = -88.0°, mp110℃,
(Racemic body: 105-106°C)) is obtained. Obtained 2-
When benzoyl-3-phenylaziridine is purified by recrystallizing it several times from methanol, it is finally [α] _D = -306.8° (C = 0.43, CHCl ₃ , pm123.5
~4.5℃). The results of IR, NMR, and CD characteristics are shown below. IR
(KBr) ν=1660 (〓C=0), 3220cm ^-1 (→
NH) NMR (CDCl ₃ ) δ = 2.5 ~ 2.7 (S, 1H,
broad, N H ), 3.2 (d, 1H, C H , J _AB =2
Hz), 3.54 (d, 1H, CH , J _AB = 2Hz), 7.4~
8.2ppm (m, 10H, Ph) CD characteristics (EtOH) [θ] ₂₃₂ = +23200, [θ] ₂₆₃
=-29700, [θ] ₃₁₅ =-13900 On the other hand, (-)-2- obtained by this Example 1
According to CRJohnson et al., the CD characteristic of (-)-(1R,2R)-trans-1-benzoyl-2-phenylcyclopropane, which has a structure very similar to benzoyl-3-phenylaziridine, is [θ] ₂₆₀ =-
25600, [θ] ₃₁₂ = −15700 (J.Amer.
Chem.Soc.1973, 95 , 4287), the absorption maximum and intensity of the CD characteristics are both extremely similar, and the absolute value of (-)-trans-2-benzoyl-3-phenylaziridine obtained in Example 1 is The body configuration is (2R, 3S). Example 2 230 mg of trans-1-benzoyl-2-phenylethylene and 346 mg ([α] _D = +
187.8°, optical purity 96.8%) and methanol 0.5ml
and stir at 50°C for 12 hours. The reaction solution was separated by column chromatography (filling material: silica gel, developing solvent: CHCl ₃ ), and (-)-(2R, 3R)-trans-2-benzoyl-3-phenylaziridine was separated.
128 mg (yield 46%, [α] _D = -87.1°, optical yield
28.4%). The same results as in Example 1 were obtained for IR, NMR, and CD characteristics. Example 3 230 mg of trans-1-benzoyl-2-phenylethylene and 346 mg of (+)-(R)-o-methoxyphenylphenylsulfuimine ([α] _D = +
187.8°, optical purity 96.8%) and methanol 0.5ml
and stir at room temperature for 6 days. The reaction solution was separated by column chromatography (filling material: silica gel, developing solvent: CHCl ₃ ), and (-)-(2R, 3R)-trans-2-benzoyl-3-phenylaziridine was separated.
148 mg (yield 53%, [α] _D = -93.3°, optical yield
30.4%). The same results as in Example 1 were obtained for IR, NMR, and CD characteristics. Example 4 230 mg of trans-1-benzoyl-2-phenylethylene and 346 mg ([α] _D = +
187.8°, optical purity 96.8%) was added to 0.3 ml of benzene and stirred at 50°C for 48 hours. The reaction solution was separated by column chromatography (filling material: silica gel, developing solvent: CHCl ₃ ), and (-)-(2R, 3R)-trans-2-benzoyl-3-phenylaziridine was separated.
268 mg (yield 96%, [α] _D = -99.9°, optical purity
32.6%). The results of IR, NMR, and CD characteristics were similar to those of Example 1. Example 5 Trans-1,2-dibenzoylethylene 295
mg and (+)-(R)-o-methoxyphenylphenylsulfuimine 346 mg ([α] _D = +164.5°,
(optical purity 84.8%) was added to 5 ml of benzene and stirred at room temperature for 1 hour. The reaction solution was subjected to column chromatography (filling material: silica gel, developing solvent;
CHCl ₃ ) to give 94 mg (-)-trans-2,3-dibenzoylaziridine (yield 30%, [α] _D =
−32.9°) is obtained. The IR and NMR results are shown below. IR (KBr) ν = 1670 [Formula] 3240 cm ^-1 (-NH) NMR (CDCl ₃ ) δ = 2.70 (S.broad,
1H, NH ), 3.73 (S, broad, 2H,
[Formula]), 7.90-8.15 (m, 4H, phenyllortho), 7.30-7.70ppm (m, 6H, phenyl
metha, para) Also, N-chloro-(-)-trans- obtained by chlorinating (-)-trans-2,3-dibenzoylaziridine obtained in Example 5
In NMR of 2,3-dibenzoylaziridine, the hydrogen signals of methine form a quartet, indicating that this aziridine is trans-isomer. NMR of N-chloro-(-)-trans-2,3-dibenzoylaziridine is shown below. MNR (CDCl ₃ ) δ = 3.37 (q, 2H,
[Formula] J _AB = 5Hz), 7.70~8.26 (m, 4H, phenylortho), 7.40~7.70ppm (m,
6H, phenylmethapara) Example 6 295 mg of cis-1,2-dibenzoylethylene and 173 mg of (+)-(R)-o-methoxyphenylphenylsulfimine ([α] _D = +187.8°, optical purity 96.8%) was added to 3 ml of benzene and stirred at room temperature for 1 hour. The reaction solution is separated by column chromatography (filling material: silica gel, developing solvent CHCl ₃ ) to obtain 124 mg (-)-trans-2,3-dibenzoylaziridine (yield 66%, optical purity -35.6°). . The same results as in Example 5 were obtained for IR and NMR. Example 7 Trans-1,2-dibenzoylethylene 295
mg and (+)-(R)-o-methoxyphenylphenylsulfuimine 346 mg ([α] _D = +187.8°,
(optical purity 96.8%) and 5 ml of dimethyl sulfoxide.
and stir at 28°C for 1 hour. The reaction solution was separated by column chromatography (filling material: silica gel, developing solvent: CHCl ₃ ), and (-)-trans-2.
3-dibenzoylaziridine 192 mg (yield 61%,
[α] _D = −20.0°) is obtained. IR and NMR are Example 5
obtained similar results. Example 8 183 mg of 1-acetyl-2-phenylethylene and 346 mg of (+)-(R)-o-methoxyphenylphenylsulfuimine ([α] _D = 164.5°, optical purity
84.8%) was added to 5 ml of benzene and stirred at 50°C for 24 hours. The reaction solution was separated by column chromatography (filling material: silica gel, developing solvent: CHCl ₃ ), and 46 mg (-)-trans-2-acetyl-3-phenylaziridine (oil, yield 23%, [α] _D =−60
゜) is obtained. The IR and NMR results are shown below. IR (neat) ν = 1700 [Formula] 3260 cm ^-1 (→NH) NMR (CDCl ₃ ) δ = 2.38 (S, 3H, C H
₃ ), 2.8 (S, 1H, NH ), 2.95 (d, 1H, C
H , J _AB = 2Hz), 3.10 (d, 1H, C H, J _AB =
2Hz), 7.1-7.5ppm (s-like, 5H, ph) Example 9 Trans-1,2-dibenzoylethylene 473
mg and (-)-(S)-o-methoxyphenylphenylsulfuimine 509 mg ([α] _D = -191.6°,
(optical purity 98.5%) was added to 3 ml of benzene and heated at 20°C.
Stir for 1 hour. The reaction solution was subjected to column chromatography (filling material: silica gel, developing solvent;
(CHCl ₃ ), 299 mg (+)-trans-2,3-dibenzoylaziridine (yield 59.4%, [α] _D
= 23.2°) is obtained. The same results as in Example 5 were obtained for IR and NMR. Example 10 417 mg of trans-1-benzoyl-2-phenylethylene and 509 mg of (-)-(S)-o-methoxyphenylphenylsulfuimine ([α] _D =-
168.5°, optical purity 86.9%) and methylene chloride 3
ml and stir at 50°C for 48 hours. The reaction solution was separated by column chromatography (filling material: silica gel, developing solvent: CHCl ₃ ), and (+)-trans-2
-Benzoyl-3-phenylaziridine 97.3mg
(Yield 21.8%, [α] _D = 77.5°) is obtained. When the obtained 2-benzoyl-3-phenylaziridine is purified by recrystallization from methanol, [α] _D = 101.9
゜was obtained. The same results as in Example 1 were obtained for IR and NMR. Example 11 trans-1-(4-methoxybenzoyl)-2
-477 mg of phenylethylene and 509 mg of (+)-(R)-o-methoxyphenylphenylsulfuilimine
([α] _D = +164.5°, optical purity 84.8%) was added to 8 ml of benzene and stirred at 50°C for 48 hours. The reaction solution was separated by column chromatography (filling material: silica gel, developing solvent: CHCl ₃ ) to give (-)-trans-2-(4-methoxybenzoyl)-3-phenylaziridine 168 mg (yield 33.2%, [α] _D = −89.5
°, mp66~67.5℃). The IR and NMR results are shown below. IR (KBr); ν=1670cm ^-1 [Formula] NMR (CDCl ₃ ); δ=2.64 (broad, 1H, NH),
3.14 (broad, 1H, CH), 3.45 (broad, 1H,
CH), 3.85 (s, 3H, OCH ₃ ), 6.85-7.32 (m,
7H, pHH), 7.97ppm (d, 2H, o-phH). Example 12 trans-1-(4-methylbenzoyl)-2-
445 mg of phenylethylene and 509 mg of (+)-(R)-o-methoxyphenylphenylsulfuimine
([α] _D = +164.5°, optical purity 84.8%) was added to 8 ml of benzene and stirred at 50°C for 48 hours. The reaction solution was separated by column chromatography (filling material: silica gel, developing solvent: CHCl ₃ ), and 237 mg (-)-trans-2-(4-methylbenzoyl)-3-phenylaziridine (yield 50%) was obtained. [α] _D = −103.5
゜) is obtained. The IR and NMR results are shown below. IR (KBr); [Formula] 3220cm ^-1 (NH). NMR (CDCl ₃ ); δ=2.46 (s, 3H, CH ₃ ),
2.46-2.95 (broad, 1H, NH), 3.29 (m, 1H,
CH), 4.12 (m, 1H, CH), 7.26-7.60 (m,
7H, pHH), 7.98ppm (d, 2H, o-phH). Example 13 trans-1-(4-bromobenzoyl)-2-
574 mg of phenylethylene and 509 mg of (+)-(R)-o-methoxyphenyl phenyl sulfilimine
([α] _D = +164.5°, optical purity 84.8%) was added to 8 ml of benzene and stirred at 50°C for 48 hours. The reaction solution was separated by column chromatography (filling material: silica gel, developing solvent: CHCl ₃ ), and 502 mg of (-)-trans-2-(4-bromobenzoyl)-3-phenylaziridine (yield: 83%) was obtained. [α] _D = -97.7°)
get. The obtained 2-(4-bromobenzoyl)-
When 3-phenylaziridine was purified by recrystallization from methanol, a product with [α] _D = -226° was obtained. The IR and NMR results are shown below. IR (KBr); [Formula] NMR (CDCl ₃ ); δ = 2.30 to 2.95 (broad, 1H,
NH), 3.20 (broad, 1H, CH), 3.45 (broad,
1H, CH), 7.10-8.10ppm (m, 9H, pHH).

Claims (1)

[Claims] 1 formula (In the formula, R ¹ and R ² represent an alkyl group, an aryl group, an alkyl-substituted aryl group, and an alkoxy-substituted aryl group, and R ³ represents hydrogen, an alkyl group, a cycloalkyl group, and an aralkyl group.) Optically active sulfylimines () having optical activity on the atom and the formula (In the formula, R ⁴ ; R ⁵ and R ⁶ represent hydrogen, an aryl group, an alkoxycarbonyl group, and an aryl carbonyl group, and R ⁷ represents an alkyl group, an aryl group, an alkyl-substituted aryl group, an alkoxy-substituted aryl group, and a halogen-substituted aryl group. group, alkoxy group.However, R ⁴ and R ⁵ are not the same. (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same as above.) A method for asymmetric synthesis of optically active aziridines ().