WO2007013697A1 - AXIS-ASYMMETRIC OPTICALLY ACTIVE QUATERNARY AMMONIUM SALT, AND PROCESS FOR PRODUCTION OF α-AMINO ACID OR DERIVATIVE THEREOF USING THE QUATERNARY AMMONIUM SALT - Google Patents

Abstract

Disclosed is a chiral phase-transfer catalyst having a simplified structure, which can be produced by reacting a 2,2'-dimethylenebromide-1,1'-binaphthyl derivative (which can be produced in relatively small numbers of steps) with a secondary amine (which is readily available). The catalyst is a compound represented by the formula (I) having a long-chain alkyl group R7 in its chemical structure. The catalyst is expected to show a high stereoselectivity even in a reaction where a conventional catalyst does not show a satisfactory stereoselectivity such as an asymmetric alkylation reaction.

Description

 Description Optically active quaternary ammonium salt having axial asymmetry and method for producing α-amino acid and derivatives thereof using the same Technical Field

 The present invention relates to an optically active quaternary ammonium salt having axial asymmetry and a method for producing the same. The present invention further relates to a method for producing an optically active amino acid and an derivative thereof using the optically active quaternary ammonium salt having this axial asymmetry as a phase transfer catalyst. Background art

The α; -alkyl monoamino acid represented by the formula H ₂ NCH (R) COOH is a very important naturally occurring amino acid. Most of a-alkyl-α_amino acids are present in animals, plants, microorganisms, etc. as L-forms having L-configuration at the α-position carbon, and this L-form constitutes a polypeptide chain. On the other hand, D form exists as a non-protein compound in plants, fungi, and microorganisms. Furthermore, α, hedialkyl _α-amino acids represented by the formula H ₂ NC (R) (R ') COOH are stereochemically stable, and when incorporated into peptides, they are enzymatically hydrolyzed by proteases. It is a compound that has been attracting attention in recent years due to its inherent function, such as being difficult to be affected (Bellier, B. et al., J. Med. Chera., 1997, 40 卷, p. 3947 and ossel, E. Et al., Tetrahedron Asymmetry, 1997, 8, p.1305). For example, it can be used as a peptide having enhanced activity, an effective enzyme inhibitor, and a chiral construct block for the synthesis of compounds having various biological activities. Such α, α-dialkyl mono α-amino acids have been studied for preparation by catalytic asymmetric reaction. No effective preparation method has been found.

 For example, chiral phase transfer catalysts that enable stereoselective alkylation of glycine derivatives are gaining importance in the field of process chemistry due to their application. To date, many studies have been conducted on the design of phase transfer catalysts, primarily using cinchona alkaloid derivatives, and several useful methods have been reported (e.g. Shioiri, T. et al., Stimulating (See Concepts in Chemistry: Vogtle, F. et al., WILEY- VCH: Weinheim, 2000, p. 123 and 0 'Donnell, MJ, Aldrichimica Acta, 2001, 34, p. 3). However, when such a phase transfer catalyst is used, there are various problems such as the use of a halogen-based solvent, a long time for the reaction, and low temperature conditions. In particular, in the above-described synthesis of α, di-alkyl-amino acids, such a chiral phase transfer catalyst derived from a cinchona al forceloid is not very useful. -The present inventors have clarified that an optically active quaternary ammonium salt having axial asymmetry can be prepared and used as a phase transfer catalyst for stereoselectively synthesizing the above-mentioned amino acids 2 0 0 1-4 8 8 6 6, JP 2 0 3 3 8 1 9 7 6, and 0oi, T. et al., J. Am. Chem. Soc., 2000, 122, (See p. 5 228). For example, the following formula:

(Wherein P h F ₃ represents a 3, 4, 5-trifluorophenyl group), a spiro-type compound represented by asymmetric double alkylation of a glycine derivative and α-alkyl-α- It is very effective for carrying out asymmetric monoalkylation of amino acid derivatives (for example, alanine derivatives). However, the preparation of such a spiro-type catalyst requires many steps. 6

 Three

When naphthol is used as the starting material, only 11 steps are required to prepare the structural part on the left side of the catalyst. As described above, the spiro-type catalyst described above has a serious drawback in that it is very time-consuming to prepare and high in cost. Disclosure of the invention

 An object of the present invention is to provide a chiral phase transfer catalyst having a simplified structure that can be produced with fewer processes. Furthermore, an object of the present invention is to provide a chiral phase transfer catalyst that can be expected to improve stereoselectivity in an asymmetric reaction by including a long-chain alkyl group in the catalyst structure.

 The present invention provides a compound represented by the following formula (I):

here,

^{R \ R 1 ', R 2} , R 2', R 3, R 3 ', R 4, R 4', R 5, R 5 ', R 6 and R ^6' are each independently,

 (i) a hydrogen atom;

(Ii) -NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently a hydrogen atom, or at any good C ₁ -C ₄ alkyl group optionally substituted by a halogen atom);

 (i i i) Siano group;

(iV) a nitro group; (v) force rubermoyl group;

 (v i) N-alkyl) a strong rubermoyl group;

(V ii) N, N-di (C ₁ -C ₄ alkyl) carbamoyl group;

(viii) one NHCOR ⁹ (wherein, R ⁹ is branched even if well and halo substituted by Gen atoms C i C alkyl group);

 (ix) may be branched or ringed and may be substituted with a halogen atom. An alkyl group of ~ ^;

(X) to form a branched or ring may be substituted in good and halogen 'atom, an alkenyl group of C ₂ -C _6;

(X i) may form a branched or cyclic and may be substituted with a halogen atom, an alkynyl group of C ₂ -C _6;

 (x i i) aralkyl group, wherein the aryl moiety constituting the aralkyl group is

May be branched and may be substituted by a halogen atom C i to C ₄ alkyl group,

Branched 'good C I～C be substituted with atoms ₅ Al' also well and halogen have Kokishi group,

Halogen atom, which may be branched and may be substituted with a halogen atom 〇 to 〇 Alkyl group, cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently , A hydrogen atom or an alkyl group which may be substituted with a halogen atom), a nitro group, a strong rubamoyl group, N— (C ₁ -C ₄ alkyl) carbamoyl group, N, N—di (C ₁ -C ₄ alkyl) a strong rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ is a C ₄ -C ₄ alkyl group which may be branched and substituted with a halogen atom). Optionally substituted, aryl group,

Ciano group, _ _NR 20 _{R 21} (wherein, R2. And R2i are each independently a hydrogen atom, or a halogen 'is either good CC alkyl group optionally substituted by atoms),

 Nitro group,

 Force rubymoyl group,

N- (C ₁ -C ₄ alkyl) force rubermoyl group,

 N, N-di (. Alkyl) force rubermoyl group,

-NHCOR ⁹ (wherein R ⁹ is a C ₁ -C ₄ alkyl group that may be branched and optionally substituted with a halogen atom), and

 Halogen atom

An aralkyl group optionally substituted with at least one group selected from the group consisting of:

 (x i i i) a heteroaralkyl group having a heteroaryl moiety, wherein the heteroaryl moiety is

 A C C alkyl group which may be branched and may be substituted by a halogen atom,

Branched c ₁ may be substituted in good and halogen atom have to c ₅ alkoxy group,

Ha port Gen atoms, may be branched and Ha port Gen atoms optionally substituted C ₄ alkyl group, 'Shiano group, one NR ^2. R ²¹ (wherein, R ²⁰ and R ²¹ are each independently a hydrogen atom, or a halogen atom is one or Ji-Ji alkyl group which may be substituted by) a nitro group, Karupamoiru group, N-(Ci C alkyl) force Rubamoiru group, N, N-di (C ₁ -C ₄ alkyl Le) force Rubamoiru group or a NHCOR ⁹ (wherein, R ⁹ is a common and halogen atoms be branched, An optionally substituted Ci CT alkyl group), an aryl group, Ciano group,

_{_NR} 20 _R 21 (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C ₄ to C ₄ alkyl group optionally substituted with a haguchi atom),

 Nitro group,

 Force rubymoyl group,

N— (C ₁ -C ₄ alkyl ') force rubamoyl group,

N, N—di (C ₁ -C ₄ alkyl) force rubamoyl group,

-NHCOR ⁹ (where, R ⁹ is Ji may be substituted with well and halogen atoms be branched ~. ^ Alkyl group), and

 Halogen atom

A heteroaralkyl group optionally substituted with at least one group selected from the group consisting of:

 (X i V) aryl group, where the aryl group is

Branched C ₁ may be substituted with at best 'and halogen atoms optionally -C ₄ alkyl group,

Branched even if well and Ha port Gen may be substituted with atoms C ~ C ₅ alkoxy group,

C ₁ -C ₄ alkyl group, Cyano group, one NR ²⁰ R ²¹ ('where R ²⁰ and R ²¹ is each independently a hydrogen atom or a Ci C alkyl group optionally substituted with a halogen atom), a nitro group, a force rubermoyl group, N- (C ₁ -C ₄ alkyl) force rubermoyl Group, N, N—di (C ₁ -C ₄ alkyl) force rubamoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and substituted with a halogen atom C ^ C An alkyl group), an aryl group, Ciano group,

_ _NR 20 _R 21 (wherein, R ²⁰ and R ²¹ are each independently a hydrogen atom, or at any good c ^ c alkyl group optionally substituted by a halogen atom),

 Nitro group,

 Force rubymoyl group,

N- (C ₁ -C ₄ alkyl) force rubermoyl group,

 N, N—di (Ci C alkyl rubamoyl group,

NHCOR ⁹ (wherein it is a Ci C alkyl group that may be branched or substituted with a halogen atom),

 A halogen atom, and

S (O) _n -R (where n is 0, 1 or 2 and R is an alkyl group which may be branched and substituted with a halogen atom)

A force that may be substituted with at least one group selected from the group consisting of: 0_ (CH ₂ ) _m -0- (where m is 1 or 2) Optionally substituted with an aryl group;

 (X V) heteroaryl group, wherein the heteroaryl group is

Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group,

A ₅ alkoxy group which may be branched and optionally substituted with a halogen atom,

A halogen atom, which may be branched and optionally substituted with a halogen atom, a CC alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently A hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a rubamoyl group, N- (Ci C alkyl) force rubermoyl group, N, N—di (ji ~. ^ Alkyl) force rubermoyl group, or one NHCOR ⁹ (where R ⁹ may be branched and has an open atom) in substituted been, also a good C ~ C ₄ alkyl group) may be substituted with, Ariru group,

 Ciano group,

_{_NR} 20 _R 21 (wherein R ² ° and R ²¹ are each independently a hydrogen atom or an alkyl group optionally substituted with a halogen atom),

 Nitro group,

 Force rubymoyl group,

N —— (C i to C ₄ alkyl) force rubermoyl group,

 N, N-di (di-alkyl) rubamoyl group,

-NHCOR ⁹ (where, R ⁹ is branched 〇 may be substituted in good and halogen atoms have ～〇 ₄ alkyl group), and

 Halogen atom

A heteroaryl group optionally substituted with at least one group selected from the group consisting of:

 (X V i) neurogenic atom;

 A group selected from the group consisting of:

R ⁷ may form a branch or a ring and may be substituted with a halogen atom C _{13 to} C ₃ . An alkyl group of

R ⁸ may form a branch or a ring, and may be substituted with a halogen atom. The alkyl group of ^, and

X scratch, halide Anion, SCN -, HS_〇 ₄ -, and a Ayuon selected from the group of HF ₂ one ing.

In one embodiment, RR ¹ ′, R ^{2 of} the compound represented by the above formula (I), R ² ′, R ³ , R ³ ′, R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′, R ⁶ and R ⁶ ′ are each independently

 (i) a hydrogen atom;

 (x i v) aryl group, where the aryl group is

Branched even if well and optionally substituted C ~ C ₄ alkyl group with a halogen atom,

Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group,

Halogen atoms, branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group, Shiano group, _NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently , A hydrogen atom or a halogen atom which may be substituted with a hydrogen atom or a halogen atom), a nitro group, a strong rubamoyl group, an N- (di-alkyl), a rubamoyl group, N, N-di ( CC alkyl) or a carbamoyl group, or one NHCOR ⁹ (wherein R ⁹ is a C i to C ₄ alkyl group which may be branched and may be substituted with a halogen atom '). You may have an ariel group,

 Ciano group,

_ _NR 20 _R 21 (where R ² ° and R ²¹ are each independently a hydrogen atom or a Ci C alkyl group optionally substituted with a haguchi atom), '

 Nitro group, '

 Carpamoyl group,

N- (C ₁ ~C ₄ alkyl) force Rubamoiru group,

N, N—di (C ₁ -C ₄ alkyl) force rubamoyl group,

-NHCOR ⁹ (wherein R ⁹ is a Ci to C ₄ alkyl group which may be branched and may be substituted with a halogen atom), Halogen atoms

-S (O) _n -R (where n is 0, 1 or 2 and R is a branched or optionally substituted alkyl group which may be substituted with a halogen atom) ;

May be substituted with at least one group selected from the group consisting of: O- (CH ₂ ) _m -0- (where m is 1 or 2 Is)

Optionally substituted by an aryl group; and

 (XV) a heteroaryl group, wherein the heteroaryl group is

 Ci C alkyl group which may be branched and may be substituted with a halogen atom,

Ci ′ to C ₅ alkoxy group which may be branched and may be substituted with a halogen atom,

アルキル基、 シァノ基、 一 NR²⁰R²¹ (ここで、 R²⁰およ び R²¹は、 それぞれ独立して、 水素原子か、 またはハロゲン'原子で置換され ていてもよい C₁〜C₄アルキル基かである） 、 ニトロ基、 力ルバモイル基、 N- (C₁〜C₄アル'キル） カルパモイノレ基、 N, N—ジ （C₁〜C₄ァノレキ ル） 力ルバモイル基、 または一 NHCOR⁹ (ここで、 R⁹は分岐していても よくかつハ口ゲン原子で置換されていてもよい C i〜 C ₄アルキル基である ) で置換されていてもよい、 ァリール基、 A halogen atom, which may be branched and substituted with a halogen atom

An alkyl group, a cyano group, one NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a C ₁ -C ₄ alkyl optionally substituted by a halogen ′ atom) N- (C ₁ -C ₄ aralkyl) carpamoinole group, N, N-di (C ₁ -C ₄ alkanol) force rubamoyl group, or one NHCOR ⁹ (wherein, R ⁹ is a is branched optionally substituted in well and Ha port Gen atoms optionally C i to C ₄ alkyl group) may be substituted with, Ariru group,

 Ciano group,

-NR ²⁰ R ²¹ (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a Ci C alkyl group optionally substituted with a haguchi atom),

Nitro group, Force rubymoyl group,

N- (C ₁ -C ₄ alkyl) force rubermoyl group,

N, N—di (C ₁ -C ₄ alkyl) carbamoyl group,

-NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and optionally substituted with a halogen atom), and

 Halogen atom

A heteroaryl group optionally substituted with at least one group selected from the group consisting of:

 A group selected from the group consisting of

In a further embodiment, the formula ^{RR 1 'R 2, R 2} ' of the compound represented by ^{(I), - R 3,} R 3 ', R 4, R 4', R 5, R 5 ', R 6 And R ⁶ ′ are each independently a hydrogen atom, 3, 4, 5_trifluorophenyl group, 3, 4, 5—trichlorophenyl group, 3, 4-difluorophenyl group, 3-nitrophenyl group, Nyl group, 3-Cyanophenyl group, Benzthiophene 2-yl group, 3, '5 -Difluoro mouth phenyl group, 3-Trifluoro mouth methyl phenyl group, 2, 4-Difluorophenyl group, 3-Methylsulfururphe -Group, 3, 5-bis (trif. Uromethinole) phenyl 'group, 4-nitrophenol group, 4-cyanophenyl group, 4-trifluoromethylphenol group, and 3,5-bis (3 ,, 5 'bis (trifluoromethyl) phenyl) selected from the group consisting of phenyl groups That is a group.

 In still another embodiment, the compound represented by the above formula (I) has the following formula:

(ここで、 ！^ぉょび尺 は、 それぞれ独立して、 水素原子、 3， 4， 5— トリフノレオロフェニル基、 3， 4， 5—トリクロ口フエニル基、 3， 4ージ フルオロフェニル '基、 3—二トロフエニル基、 3—シァノフエ二ル'基、 ベン ゾチォフエニル一 2—ィル基、 3, 5—ジフノレオロフェニル '基、 3—トリフ ルォロメチルフエニル基、 2, 4—ジフル'オロフェニル基、 3—メチルスル ホニルフエニル基、 3， 5—ビス （トリフルォロメチルう フエニル基、 4一 ニトロフエニル基、 4一シァノフエニル基、 4一トリフルォロメチルフエ二 ル基、 および 3 , 5—ビス （ 3， ， 5， 一ビス （トリフルォロメチル） フェ -ル） フヱニル基からなる群より選択される基であり、 そして R⁷、 R⁸およ び X—は、 それぞれ独立して、 上記式 （ I ) で表される化合物と同様に定義 される基である） で表される化合物である。

(Where, ^^ is a hydrogen atom, 3, 4, 5— trifnoleolophenyl group, 3, 4, 5— trichlorophenyl group, 3, 4-difluorophenyl. 'Group, 3-diphenyl group, 3-cyanophenyl' group, benzothiophenyl-1-yl group, 3,5-diphenylolphenyl 'group, 3-trifluoromethylphenyl group, 2, 4 —Difluoro'ophenyl group, 3-methylsulfonylphenyl group, 3,5-bis (trifluoromethyl uphenyl group, 4-1-nitrophenyl group, 4-1-cyanophenyl group, 4-1-trifluoromethylphenyl group, and 3, 5-bis (3,5, monobis (trifluoromethyl) phenyl) group selected from the group consisting of phenyl groups, and R ⁷ , R ⁸ and X— are each independently And the compound represented by the above formula (I) A compound represented by a group) similarly defined.

In one embodiment, R ⁷ of the compound represented by the formula (I) is a C _{13 to} C ₂₂ alkyl group which may form a branch or a ring.

In a further embodiment, R ⁷ and R ⁸ of the compound represented by formula (I) are the same.

 The present invention also provides a method for producing a compound represented by the above formula (I), which comprises the following formula (I I):

In the presence of an acid scavenger in an organic solvent, the compound represented by

The following formula (I I I): p7

8 (III) A step of reacting with a secondary amine represented by:

Where in formula (I I)

^{R \ R 1 ', R 2} , R 2', R 3, R 3 ', R 4, R 4', R 5, R 5 ', R 6 and R ^6' are each independently,

 (i) a hydrogen atom;

(ii) -NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a C to C ₄ alkyl group optionally substituted with a haguchigen atom) ;

 (i i i) Siano group;

 (i v) a nitro group;

 (V) a carpamoyl group;

 (V i) N- (di-alkyl) carbamoyl group;

 (V i i) N, N-di (Ci C alkyl) force rubermoyl group;

(viii) -NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group that may be branched and optionally substituted with a halogen atom);

(Ix) may form a branched or cyclic and may be substituted with a halogen atom, an alkyl group of C ₁ -C _6;

(X) and it may form a branched or ring may be substituted with C port Gen atoms, alkenyl group of C ₂ -C _6;

(X i) may form a branched or cyclic and may be substituted with a halogen atom, an alkynyl group of C ₂ -C _6;

 (X i i) aralkyl group, wherein the aryl moiety constituting the aralkyl group is

Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group,

C _{1 to} C ₅ may be branched and may be substituted with a halogen atom An alkoxy group,

A halogen atom, which may be branched and substituted with a halogen atom, a Ci C alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are Independently, a hydrogen atom or a halogen atom that may be substituted with an alkyl group), a nitro group, a strong rubamoyl group, N- (CC alkyl) a strong rubamoyl group, N, N-di (C ₁ -C ₄ alkyl le ') force Rubamoiru group or a NHCOR ⁹ (where,, R ⁹ is a branched even if well and Ha port Gen atoms optionally substituted C ~ C ₄ alkyl group An aryl group, which may be substituted with

 Ciano group,

_{_NR} 20 _R 21 (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C ₄ to C ₄ aralkyl group optionally substituted with a haguchi atom) ,

 Nitro group,,

 Force rubymoyl group,

 N— (ji-ji alkyl ') rubamoyl group,

N, N—di (C ₁ -C ₄ ar'kyl) carbamoyl group,

-NHCOR ⁹ (wherein R ⁹ is a C ₁ -C ₄ alkyl group which may be branched and optionally substituted with a halogen atom), and '

 Halogen atom

An aralkyl group optionally substituted with at least one group selected from the group consisting of:

 (x i i ί) a heteroaralkyl group having a heteroaryl moiety, τ, wherein the heteroaryl moiety is

An alkyl group which may be branched and optionally substituted with a haguchigen atom, C Cs alkoxy group which may be branched and may be substituted with a halogen atom, halogen atom, CC alkyl group which may be branched and which may be substituted with a halogen atom, a cyano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently a hydrogen atom, or at any good C ₁ -C ₄ alkyl group optionally substituted by a halogen atom), a nitro group, a force Rubamoiru group, N- (. ~. alkyl) force Rubamoiru group, N, N-di (C ₁ -C ₄ alkyl Le) force Rubamoiru group or a NHCOR ⁹ (where,, R ^9, which may be branched And an alkyl group that may be substituted with a halogen atom), an aryl group,

 Ciano group,

_ _nr20r21 (wherein R ² and R ²¹ are each independently a hydrogen atom or a ₄ alkyl group optionally substituted with a halogen atom),

 Nitro group,

 Carpamoyl group,

N— (C ₁ -C ₄ alkyl.) Force rubamoyl group,

N, N-di (C ₁ -C ₄ alkyl ') force Rubamoiru group,

-NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and

 Halogen atom

A heteroaralkyl group optionally substituted with at least one group selected from the group consisting of:

(x i v) aryl group, where the aryl group is

Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group, Ci Cs alkoxy group which may be branched and may be substituted with a halogen atom,

A halogen atom, which may be branched and optionally substituted with a halogen atom, an alkyl group, a cyano group, one NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom; Or an alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl group, N— (C ₁ -C ₄ alkyl) a strong rubamoyl group, N, N—di (di-alkyl) R ′) substituted with a strong rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and substituted with a halogen atom and may be a C to C ₄ alkyl group). You may have an ariel group,

 Ciano group,

-NR ²⁰ R ²¹ (wherein, R ^2C) and R ²¹ are each independently either hydrogen atom, or at any good C ₁ -C ₄ alkyl group optionally substituted by a halogen atom),

 Nitro group,

 Force rubymoyl group,

 N—alkyl) strong rubermoyl group,

N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

-NHCOR ⁹ (wherein R ⁹ is a c ₁ -c ₄ alkyl group which may be branched and may be substituted with a halogen atom),

 A halogen atom, and

-S (O) _n -R (where n is 0, 1 or 2 and R is a Ci C alkyl group which may be branched and substituted with a halogen atom)

At least one or which may be substituted with a group selected from the group consisting of, or 3, 4 Tsute 〇 one such together form (CH _{2) m} -0- (wherein m is 1 or Or an aryl group which may be substituted with

 (XV) heteroaryl group, wherein the heteroaryl group is

 Ci C alkyl group which may be branched and may be substituted with a halogen atom,

Branched even if well and Ha port Gen atoms optionally substituted c ₁ to c ₅ alkoxy group, a halogen atom, branched even if well and good Ci C alkyl group optionally substituted by a halogen atom, Shiano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently a hydrogen atom, or is or may 〇 ～〇 alkyl group which may be substituted by a halogen atom), Nitro group, strong rubermoyl group, N- (di ^ ~ di ^ alkyl) carbamoyl group, N, N-di (di-alkyl) force rubamoyl group, or one NHCOR ⁹ (where R ⁹ is branched) A Ci C alkyl group which may be substituted with a halogen atom and may be substituted with an aryl group,

 Ciano group, '

_ _{nr20r2 I} (wherein R ² and R ²¹ are each independently a hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom),

 Nitro group,

 Canolebakyl group,

 N—alkyl) strong rubermoyl group,

N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

-NHCOR ⁹ (where, R ⁹ is branched c ₁ may be substituted in good and halogen atom have to c ₄ alkyl group), and

 Neurogen atom

Optionally substituted with at least one group selected from the group consisting of A teloaryl group; and

 (X V i) halogen atom;

 A group selected from the group consisting of and

Z is a halogen atom,

And in the formula (I I I)

R ⁷ may form a branch or a ring and may be substituted with a halogen atom C _{13 to} C ₃ . An alkyl group of

R ^8, which may be branched or form a ring and may be substituted by a halogen atom, an alkyl group of C Cso.

In one embodiment, I ¹ , R ¹ ′, RR ² ′, −R ³ , R ³ ′, R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′, of the compound represented by the above formula (II), R ⁶ and R ⁶ ′ are independent

 (i) a hydrogen atom;

 (X i V) an aryl group, wherein the aryl group is 'optionally branched' and optionally substituted with a halogen atom,

_May be branched and may be substituted with a halogen atom;

Halogen atoms, branched C ₁ -C ₄ optionally substituted at good and halogen atoms have an alkyl group, Shiano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently And may be substituted with a hydrogen atom or a halogen atom. ~ 〇 Alkyl group), nitro group, force rubamoyl group, N- (Ci C alkyl) carbamoyl group, N, N-di ( C ₁ -C ₄ alkyl Le) force Rubamoiru group or a NHCOR ⁹ (wherein, in R ⁹ is branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group) Optionally substituted, aryl group, Ciano group,

-NR ²⁰ R ²¹ (wherein R ^{2 G} and R ²¹ are each independently a hydrogen atom or a Ci to C ₄ alkyl group optionally substituted with a haguchi atom),

 Nitoguchi,

 Force rubymoyl group,

 N— (ji ~. ^ Alkyl) force rubermoyl group,

N, N-di (C ₁ -C ₄ alkyl.) Karupamoiru group,

-NHCOR ⁹ (wherein R ⁹ is a C ₄ to C ₄ alkyl group which may be branched and may be substituted with a halogen atom),

 Halogen atoms and

- in S (O) _n -R (wherein, n is 0, 1 or 2, and R is a branch and may have and Ci~C may be substituted with a halogen atom ₄ alkyl Le group is there) ;

May be substituted with at least one group selected from the group consisting of: or O- (CH ₂ ) _m -0- (where m is 1 or 2)

Optionally substituted by an aryl group; and

 (X V) heteroaryl group, which is

 An alkyl group which may be branched and optionally substituted with a halogen atom,

Branched even if well and halogen 'in atom substituted. Which may be C i~C ₅ alkoxy group,'

Halogen atoms, branched and have good and optionally substituted Ci C alkyl group by a halogen atom, Shiano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently, Substituted by hydrogen atom or halogen atom Even if it is good or Ci C alkyl group), a nitro group, a force Rubamoiru group, N-(~ Ji alkyl) force Rubamoiru group, N, N-di (C ₁ -C ₄ alkyl le ') force Rubamoiru group, or a NHCOR ⁹ (wherein, R ⁹ is substituted with branched even if well and halogen atoms is also good C ₁ -C ₄ alkyl group). may be substituted with, Ariru group,

 A cyano group,

_ _{Nr 2 0 r} 21 (wherein, R ² ° and R ²¹ are each independently a hydrogen atom, or a good or C! ~ C ₄ alkyl group is optionally substituted by C port Gen atoms) ,

 Nitro group,

 Cal 'bamoyl group,

N— (C ₁ -C ₄ alkyl) force rubamoyl group,

N, N—di (C ₁ -C ₄ alkyl) force rubamoyl group,

-NHCOR ⁹ (wherein R ⁹ is a C ₁ -C ₄ alkyl group that may be branched and optionally substituted with a halogen atom), and

 Halogen atom

A heteroaryl group optionally substituted with at least one group selected from the group consisting of:

 A group selected from the group consisting of

In a further embodiment, the formula ^{RR 1 'R 2, R 2} ' of the compound represented by ^{(II), R 3, R} 3 ', R 4, R 4', R 5, R 5 ', R 6 and R ⁶ 'is their respective independently a hydrogen atom, 3, 4, 5-trifluorophenyl group, 3, 4, 5-trichloro port phenyl group, 3, 4-diphenyl Honoré Oro phenylene Honoré group, 3- Nitrophenyl group, 3-cyanophenyl group, benzothiophenyl-2-yl group, 3,5-difluorophenyl 'group, 3-trifluoromethylphenyl group, 2,4-difluorophenylol group, 3- Methinolesulfonino fenenole group, 3,5-bis (Trifluoromethyl) phenyl group, 4_nitrophenyl group, 4-cyanophenyl group, 4_trifluoromethylphenyl group, and 3,5-bis (3,5'-bis (trifluoromethyl) phenyl) It is a group selected from the group consisting of phenyl groups.

 In still another embodiment, the compound represented by the above formula (I I) has the following formula (11,):

(ΙΙ')

(ΙΙ ')

(Wherein, - R ¹ and R ¹ 'are each independently a hydrogen atom, 3, 4, 5-trifluorophenyl group, 3, 4, 5-trichloro port Hue - group, 3, 4-di Fluorophenyl group, 3-diphenyl group, 3-cyanophenyl group, benzothiophenyl 2-yl group, 3,5-difluorophenyl group, 3-trifluoromethylphenyl group, 2,4-difluorophenyl group , 3-methylsulfurphenyl group, 3,5-bis (trifluoromethyl) phenyl group, 4_ nitrophenyl group, 4-cyanophenenyl group, 4-trifluoromethylphenyl group, and 3,5-bis ( 3 ', 5, one bis a (triflate Ruo ii methyl) Hue) group is selected from the group consisting of phenyl group, and R ^7, R ⁸ and Z are each independently formula (II ) Is defined in the same way as the compound represented by Is a compound represented by the following formula:

In one embodiment, the secondary amine R ⁷ represented by the above formula (II) may form a branch or a ring, C! _{3 to} C ₂₂ alkyl ¾.

In a further embodiment, R ⁷ and R ^{8 of the} secondary amine represented by the above formula (II) are the same.

The present invention also provides a compound represented by the formula (VI):

A method for stereoselectively producing

 Pure formula for axial asymmetry (I):

A compound represented by formula (IV) using a compound as a phase transfer catalyst:

A compound of formula (V) in the presence of an inorganic base in a medium:

R ¹⁸ -W (V)

Alkylating with:

 Where in formula (I)

R ¹ R ¹ ′, R ² , R ² ′, R ³ , R ³ ′, R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′, R ⁶ and R ⁶ ′ are each independently

 (i) a hydrogen atom;

(ii) -NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a Ci C alkyl group which may be substituted with a halogen atom);

(iii) a cyano group; (iv) a nitro group;

 (V) force rubamoyl group;

 (V i) N- (ji-ji alkyl) force rubamoyl group;

(V ii) N, N- di (C ₁ -C ₄ alkyl) Karupamoiru group; '

(viii) -NHCOR ⁹ (wherein R ⁹ is a C 1 -C ₄ alkyl group which may be branched and optionally substituted with a halogen atom);

(Ix) may form a branched or cyclic and may be substituted with a halogen atom, an alkyl group of C ₁ -C _6;

(X) may form a branched or cyclic and may be substituted with a halogen atom, an alkenyl group of C ₂ -C _6;

(xi C ′ ₂ -C ₆ alkynyl group which may form a branch or ring and may be substituted with a halogen ′ atom;

(xii) an aralkyl group, wherein the aryl moiety constituting the aralkyl group is: a C ₁ -C ₄ alkyl group that may be branched and substituted with a halogen atom,

Ci C ₅ alkoxy group which may be branched and may be substituted with a halogen atom,

Halogen atoms, branched C ₁ -C ₄ optionally substituted at good and halogen atoms have an alkyl group, Shiano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently A hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl group, an N- (C ₁ -C ₄ alkyl) carbamoyl group, N , N-di (C ₁ -C ₄ alkyl) force rubamoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and may be substituted with a halogen atom. An aryl group, which may be substituted with Ciano group,

_{_NR} 20 _R 21 (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a ₄ alkyl group optionally substituted with a haguchi atom),

 Nitro group,

 Force rubymoyl group,

N- (C ₁ -C ' ₄ alkyl) force rubamoyl group,

N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

— NHCOR ⁹ (wherein R ⁹ is optionally branched and substituted with a halogen atom to an alkyl group), and

 Halogen atom

An aralkyl group optionally substituted with at least one group selected from the group consisting of:

 (x i i i) a heteroaralkyl group having a heteroaryl moiety, wherein the heteroaryl moiety is

Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group,

May be branched and may be substituted by a halogen atom C -C ₅ alkoxy group,

Halogen atoms, branched C ₁ -C ₄ optionally substituted at good and halogen atoms have an alkyl group, Shiano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently It may be substituted with a hydrogen atom or a halogen atom, which is an alkyl group), a nitro group, a strong rubamoyl group, N- (Ci C alkyl) a strong rubamoyl group, N, N-di (Ji-jikyl) force rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ is a C ₁ -C ₄ alkyl group which may be branched and may be substituted with a halogen atom) Optionally substituted with an aryl group,

 Ciano group,

-NR ²⁰ R ²¹ (wherein 1 ^{2 () and} 11 ²¹ are each independently a hydrogen atom or a C to C ₄ alkyl group optionally substituted with a halo atom) ),

 Nitro group,

 Carpamoyl group,

 N- (Ci C alkyl) strong rubermoyl group,

 N, N—di (dialkyl), rubamoyl group,

-NHCOR ⁹ (wherein R ⁹ is a C ₁ -C ₄ alkyl group that may be branched and optionally substituted with a halogen atom), and

 Neurogen atom

A heteroaralkyl group optionally substituted with at least one group selected from the group consisting of:

 (X i V) aryl group, where the aryl group is

 An alkyl group which may be branched and optionally substituted with a halogen atom,

Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group,

A halogen atom, which may be branched and optionally substituted with a halogen atom, a Ci C alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently hydrogen atom or is either an alkyl group which may be substituted by a halogen atom), a nitro group, a force Rubamoiru group, N-(0 ～〇 ₄ alkyl) force Rubamoiru group, N, N-di (C ₁ ~ C ₄ alkyl) a strong rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ is a C ₄ to C ₄ alkyl group which may be branched and may be substituted with a divalent atom) Optionally substituted with an aryl group,

 Ciano group,

-NR ²⁰ R ²¹ (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C to C ₄ alkyl group optionally substituted with a halo atom),

 Nitoguchi,

 Force rubymoyl group,

 N- (C ^ C alkyl) strong rubermoyl group,

N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

-NHCOR ⁹ (wherein R ⁹ is a C ₁ -C ₄ aralkyl group which may be branched and may be substituted with a halogen atom),

 A halogen atom, and

One S (O) _N- R (wherein n is 0, 1 or 2 and R is a C _{4 to} C ₄ alkyl group which may be branched and substituted with a halogen atom) is there)

May be substituted with at least one group selected from the group consisting of or O- (CH ₂ ) _m -0- (where m is 1 or 2 Which may be substituted with an aryl group;

 (X V) a heteroaryl group, which is

 An alkyl group which may be branched and optionally substituted with a halogen atom,

Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group,

Halogen atom, which may be branched and optionally substituted with a halogen atom 〇 to 〇 Alkyl group, cyano group, _NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are independently Substituted by hydrogen atom or halogen atom Which may be c ₁ to c is ₄ or alkyl group), a nitro group, a force Rubamoiru group, N- (C ₁ ~C ₄ alkyl) force Rubamoiru group, N, N-di (Ci C alkyl Le) force Rubamoiru A group, or one NHCOR ⁹ wherein R ⁹ is a Ci CT alkyl group which may be branched and optionally substituted with a halogen atom, an aryl group,

 Ciano group,

-NR ²⁰ R ²¹ (wherein R ^2Q and R ²¹ are each independently a hydrogen atom or a C! To C ₄ alkyl group optionally substituted with a halo atom),

 Nitoguchi,

 Force rubermoyl 'group,

N- (C ₁ ~C ₄ alkyl) force Rubamoiru group,

N, N—di (C ₁ -C ₄ alkyl) carbamoyl group,

-NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and substituted with a halogen atom), and

 Halogen atom

A heteroaryl group optionally substituted with at least one group selected from the group consisting of:

 A group selected from the group consisting of forces,

R ⁷ may form a branch or a ring, and may be substituted with a halogen atom C _{13 to} C ₃ . An alkyl group of

R ⁸ is an alkyl group which may form a branch or a ring and may be substituted with a halogen atom,

 X-is a halide anion,

In formula (IV) and formula (V I),

R ¹⁴ and R ¹⁵ are each independently (i) a hydrogen atom; or

 (i i) an aryl group, the aryl group

アルキル基、 May be branched and may be substituted with a halogen atom c

An alkyl group,

A C to C ₅ alkoxy group which may be branched and optionally substituted with a halogen atom,

Halogen atom, which may be branched and optionally substituted with a halogen atom CC alkyl group, cyano group, one NR ³⁰ R ³¹ (where R ³⁰ and R ³¹ are each independently hydrogen N- (C ₁ -C ₄ alkyl) force rubamoyl group, N, N-di (C!), Or a CC alkyl group optionally substituted by an atom or a halogen atom) C alkyl) substituted with a strong rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ is a C ₄ to C ₄ alkyl group which may be branched and optionally substituted with a halogen atom). Maybe, Aryl group,

 Ciano group,

_{_NR} 30 _R 31 (wherein R ³ ° and R ³¹ are each independently a hydrogen atom or a Ci C alkyl group optionally substituted with a haguchi atom),

 Nitro group,

 Power Luba Nyl group,

Ν- (C ₁ -C ₄ alkyl) force rubamoyl group,

 N, N—di (di- ^ alkyl) force rubermoyl group,

-NHCOR ⁹ (where, R ⁹ is branched c ₁ may be substituted in good and halogen atom have to c ₄ alkyl group), and

 Halogen atom

May be substituted with at least one group selected from the group consisting of A linear group;

Except that R ¹⁴ and R ¹⁵ are both hydrogen atoms, R ¹⁶ is

 (i) a hydrogen atom;

(ii) an alkyl group and may form a branched or cyclic optionally substituted by a halogen atom C ₁ -C ₁ Q, the alkyl group,

Branched c ₁ may be substituted in good and halogen atom have to c ₅ alkoxy group,

 Ciano group,

NR ³ ° R ³¹ (wherein R ³ ° and R ³¹ are each independently a hydrogen atom or an alkyl group which may be substituted with a halogen atom),

 Nitro group,

 Force rubymoyl group,

N- (C ₁ ~C ₄ alkyl) Karupamoiru group,

N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

-NHCOR ⁹ (wherein R ⁹ is a Ci to C ₄ alkyl group which may be branched and may be substituted with a halogen atom),

 Neurogenic atom,

-COR ⁹ (wherein R ⁹ is a c ₁ -c ₄ alkyl group which may be branched and optionally substituted with a halogen atom), and

アルキル基である） — C0 ₂ R ⁹ (where R ⁹ may be branched and substituted with a halogen atom)

An alkyl group)

An alkyl group optionally substituted with at least one group selected from the group consisting of:

(iii) may be branched or ring and substituted with a halogen atom An alkenyl group of c _{2 to} c ₆ , which may be

(I V) to form a branched or ring may be substituted with at best force halogen atom, an alkynyl group of C ₂ -C _6;

 (V) an aralkyl group, wherein the aryl moiety constituting the aralkyl group may be branched and substituted with a halogen atom. An alkyl group,

アルキル基、 シァノ基、 一 NR²⁰R²¹ (ここで、 R²⁰およ び R²¹は； それぞれ独立して、 水素原子か、 またはハロゲン原子で置換され ていてもよい Ci C アル.キル基かである） 、 ニトロ基、 力ルバモイル基、 N— （C₁〜C₄アルキルう 力ルバモイル基、 N， N—ジ アルキ ル'） 力ルバモイル基、 または一 NHCOR⁹ (ここで、 R⁹は分岐してい も よくかつハ口ゲン原子で置換されていてもよい C i〜 C ₄アルキル基である） で置換されていてもよい、 ァリール基、 ₅ may be branched and may be substituted with a halogen atom ₅ alkoxy group, halogen atom, may be branched and may be substituted with a halogen atom

An alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently a hydrogen atom or a Ci C alkyl group optionally substituted with a halogen atom) ), A nitro group, a strong rubamoyl group, N— (C ₁ -C ₄ alkyl rubamoyl group, N, N—dialkyl ′) a strong rubamoyl group, or one NHCOR ⁹ (where R ⁹ is branched) A C 1 -C ₄ alkyl group which may be substituted with a divalent atom, and may be substituted with an aryl group,

 Ciano group,

_ _NR 20 _R 21 (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a C ₄ to C ₄ alkyl group optionally substituted with a halogen atom), '

 Nitro group,

 Force rubymoyl group,

N— (C ₁ -C ₄ alkyl) force rubamoyl group,

N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

-NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and Halogen atom

May be substituted with at least one group selected from the group consisting of, and the alkyl moiety constituting the aralkyl group may form a branch or a ring and be substituted with a halogen atom. An aralkyl group which is a c ₁ -c ₆ alkyl group;

 (v i) a heteroaralkyl group having a heteroaryl moiety, wherein the heteroaryl moiety is

Branched even if well and optionally substituted C ~ C ₄ alkyl group with a halogen atom,

A ci to C ₅ alkoxy group which may be branched and optionally substituted with a halogen atom,

A halogen atom, which may be branched and substituted with a halogen atom, a Ci C alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are independently, either a hydrogen atom, or is or a halogen atom substituted expired C ₁ optionally -C ₄ alkyl group), a nitro group, a force Rubamoiru group, N- (〇 ～〇 alkyl) Karupamoiru group, N, N-di (. ~ Alkynole) Carpamoyl group, or one NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom) It ’s good.

 Ciano group,

_{_NR} 20 _R 21 (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a _4- alkyl group optionally substituted with a haguchi atom),

 Nitro group,

 Force / Leva Moinole group,

N—alkyl) strong rubermoyl group, N, N-di (C 1 -C ₄ alkyl) force rubamoyl group,

-NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and

 Halogen atom

A heteroaralkyl group optionally substituted with at least one group selected from the group consisting of:

 (V i i) 'Allele group,

 Ci C alkyl group which may be branched and may be substituted with a halogen atom,

 A C Cs alkoxy group which may be branched and may be substituted with a halogen atom,

A halogen atom, which may be branched and may be substituted with a halogen atom, an alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently , A hydrogen atom or an alkyl group which may be substituted with a halogen atom), a utro group, a carb'moyl group, an N— (C ₁ -C ₄ alkyl) force rubamoyl group, an N, N— Di (C ₁ -C ₄ alkynole) force rubamoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and may be substituted with a halogen atom. It is an alkyl group) Optionally substituted with an aryl group,

 Ciano group,

_{_NR 2} O _r21 (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a Cj to C ₄ alkyl group optionally substituted with a halogen atom), ■ ■

 Nitro group,

 Force rubymoyl group,

N— (C ₁ -C ₄ alkyl group rubamoyl group, N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

-NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and

 Halogen atom

An aryl group optionally substituted with at least one group selected from the group consisting of:

 (V i i i) a heteroaryl group, wherein the heteroaryl group may be branched and substituted with a halogen atom,

Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group,

Halogen atoms, branched C ₁ -C ₄ optionally substituted at good and halogen atoms have an alkyl group, Shiano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently A hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl group, N— (Ci C alkyl) a strong rubamoyl group, N, N —Di (C ₁ -C ₄ alkyl) force ruberamoire group, or one NHCOR ⁹ (wherein R ⁹ is a Ci-C ₄ alkyl group which may be branched and may be substituted with a halogen atom) ) May be substituted with an aryl group,

 Ciano group,

_ _NR 20 _R 21 (wherein, R20 and R2i are each independently a hydrogen atom. Or is or may Ji-Ji alkyl group which may be substituted by a halogen atom),

 Nitro group,

 Force rubymoyl group,

N— (ji ~! ^! Alkyl) force rubermoyl group, N, N—di (〇 to 〇 ₄ alkyl ') force rubamoyl group,

-NHCOR ⁹ (wherein R ⁹ is a 0 to 0 alkyl group which may be branched and may be substituted with a halogen atom), and

 Halogen atom

A heteroaryl group optionally substituted with at least one group selected from the group consisting of:

 A group selected from the group consisting of forces,

R ¹⁷ is a C _{1 to} C ₈ alkyl group which may form a branch or a ring and may be substituted with a halogen atom;

In equations (V) and (V I)

R ^18-

(i) C Ci which may form a branch or a ring and may be substituted with a halogen atom. Wherein the alkyl group is

 C i Cs alkoxy group which may be branched and may be substituted with a halogen atom,

 Ciano group,

_{_NR} 30 _R 31 (wherein R ³ ° and R ³¹ are each independently a hydrogen atom or a C i to C ₄ alkyl group optionally substituted with a haguchi atom),

 Nitro group,

 Force rubymoyl group,

 • N— (ji-ji alkyl) force rubermoyl group,

N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

-NHCOR ⁹ (wherein R ⁹ is a CC alkyl group which may be branched and may be substituted with a halogen atom),

Halogen atom -COR ⁹ (wherein R ⁹ is a c ₁ -c ₄ alkyl group which may be branched and optionally substituted with a halogen atom), and

1 C 0 ₂ R ⁹ (wherein R ⁹ may be branched and substituted with a halogen atom)

An aralkyl group optionally substituted with at least one group selected from the group consisting of:

(Ii) may form a branched or cyclic and may be substituted by halogen atom, Ariru or substituted Ariru group C ₃ -C _9;

And (iii) to form a branched or ring may be substituted with at best force halogen 'atom, an alkenyl group of C ₂ -C _6;

(I V) to form a branched or ring may be substituted in good and halogen atom, an alkynyl group of c ₂ to c _6;

アルキル基、 (V) an aralkyl group, wherein the aryl moiety constituting the aralkyl group may be branched and may be substituted with a halogen atom

An alkyl group,

A C to C ₅ alkoxy group which may be branched and optionally substituted with a halogen atom,

A halogen atom, which may be branched and optionally substituted with a halogen atom, a Ci C alkyl group, a cyano group, one NR ²⁰ R ²¹ (where, R ²⁰ and R ²¹ are each independently , A hydrogen atom, or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl group, N — (.- alkyl) a strong rubamoyl group, N, N—di (Ji-Ji alkinore) substituted with a strong rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ is a Ci C ₄ alkyl group which may be branched and may be substituted with a divalent atom) May have been, allyl group,

Ciano group, One NR ² ° R ²¹ (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C to C ₄ alkyl group optionally substituted with a haguchi atom),

 Nitro group,

 Force rubymoyl group,

 N— (Ci C alkyl) force rubermoyl group,

N, N—di (〇 to 〇 ₄ alkyl) group

-NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and

 Halogen atom

May be substituted with at least one group selected from the group consisting of, and the alkyl moiety constituting the aralkyl group may form a branch or a ring and be substituted with a halogen atom. May be a C to C ₆ alkyl group, an aralkyl group;

 (V i) A heteroaralkyl group having a heteroaryl moiety, wherein the heteroaryl moiety is

 An alkyl group which may be branched and may be substituted with a halogen atom;

Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group,

A halogen atom, which may be branched and optionally substituted with a halogen atom, a Ci C alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently A hydrogen atom, or a Ci C alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl group, N— (Ci C ^ alkyl) a strong rubamoyl group, N, N—di丄 ~. ^ Alky Nole) Force rubermoyl group, or one NHCOR ⁹ (where R ⁹ is branched A C 1 -C ₄ alkyl group which is optionally substituted with a halo atom, and may be substituted with an aryl group,

 Ciano group,

_ _NR 20 _{R 2 1} (wherein R 20 and; are each independently a hydrogen atom or a halogen atom, which may be a 4- to _4- alkyl group),

 Nitro group,

 Force rubymoyl group,

N- (C ₁ ~C ₄ alkyl power sale power Rubamoiru group,

 N, N—di (C C ar'kyl) carbamoyl group,

-NHCOR ⁹ (where, R ⁹ is branched c ₁ may be substituted in good and halogen atom have to c ₄ alkyl group), and

 Halogen atom

A heteroalkyl group optionally substituted with at least one group selected from the group consisting of:

(V ii) may be branched and may be substituted with a halogen atom, C ₃ to C ₉ propargyl group or substituted propargyl group;

 A group selected from the group consisting of:

In equation (V)

w is a functional group having a leaving ability,

And in the formula (V I)

 * Indicates a newly generated asymmetric center.

In one embodiment, RR ¹ ′, R of the compound represented by the above formula (I)

R ² ′, R ³ , R ³ ′, R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′, R ⁶ and R ⁶ ′ are each independently

(i) a hydrogen atom; (xiv) an aryl group, wherein the aryl group is

 A C C alkyl group which may be branched and optionally substituted with a halogen atom,

Branched even if well and Ha port gen atoms may be substituted by C ~ C ₅ Anorekokishi group,

アルキル基、 シァノ基、 一 NR²⁰R²¹ (ここで、 R²⁰およ び R²¹は、 それぞれ独立して、 水素原子か、 またはハロゲン原子で置換され ていてもよい Ci〜C₄アルキル基かである） 、 ニトロ基、 力ルバモイル基、 N- (C^ C アルキル.） 力ルバモイル基、 N, N—ジ （じ 〜じ アルキ ル） 力ルバモイル基、 または一 NHCOR⁹ (ここで、 . R⁹は分岐していても よくかつハロゲン原子で置換されていてもよい Ci C アルキル基である） で置換されていてもよい、 ァリール基、 A haguchigen atom, which may be branched and substituted with a haguchigen atom C

Alkyl group, cyano group, one NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a Ci to C ₄ alkyl group optionally substituted with a halogen atom) ), A nitro group, a rubamoyl group, N- (C ^ C alkyl.) A rubamoyl group, N, N-di (di-alkyl) rubamoyl group, or one NHCOR ⁹ (where .R ⁹ is a Ci C alkyl group that may be branched and optionally substituted with a halogen atom), an aryl group,

 Ciano group,

_{_NR} 20 _R 21 (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C ₄ to C ₄ alkyl group optionally substituted with a haguchi atom),

 Nitoguchi,

 Carpamoyl group,

N- (C ₁ ~C ₄ alkyl) Karupamoiru group,

N, N—di (C ₁ -C ₄ alkyl) carbamoyl group,

-NHCOR ⁹ (wherein R ⁹ is a c ₁ -c ₄ alkyl group which may be branched and may be substituted with a halogen atom),

 Halogen atoms

-S (O) _n -R (where n is 0, 1 or 2 and R may be branched and substituted with a halogen atom Ci C alkyl Group);

May be substituted with at least one group selected from the group consisting of: O— (CH ₂ ) _m -0- (where m is 1 or 2 Is)

Optionally substituted by an aryl group; and

 (XV) a heteroaryl group, wherein the heteroaryl group is

 It may be branched and may be substituted with a halogen atom. ^ Alkyl group,

Ci C ₅ alkoxy group which may be branched and may be substituted with a halogen atom,

Halogen atoms, branched C ₁ -C ₄ optionally substituted at good and halogen atoms have an alkyl group, Shiano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently and, either a hydrogen atom, or at or even better C ₁ -C ₄ alkyl group optionally substituted by a halogen atom), a nitro group, a force Rubamoiru group, N- (C ₁ ~C ₄ alkyl cormorants Karupamoiru group, N , N-di (C ₁ -C ₄ alkyl) force rubamoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and may be substituted with a halo atom C ₁ -C _An alkyl group), an aryl group,

 Ciano group,

_{_NR} 20 _R 21 (wherein R ² ° and R ² i are each independently a hydrogen atom or a C to C ₄ alkyl group optionally substituted with a haguchi atom),

 Nitro group,

 Carpamoyl group,

N- (C ₁ ~C ₄ alkyl) force Rubamoiru group,

N, N-di (C, ~ C ' ₄ alkyl) force rubamoyl group, -NHCOR ⁹ (wherein R ⁹ is a C ^ C alkyl group which may be branched and optionally substituted with a halogen atom), and

 Halogen atom

A heteroaryl group optionally substituted with at least one group selected from the group consisting of:

A group selected from the group consisting of

In a further embodiment, RR ¹ ′ ^ R ² , R ² ′, R ³ , R ³ ′, R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′, R ^{6 of the} compound represented by the above formula (I) And R ⁶ ′ each independently represents a hydrogen atom, 3, 4, 5-trifluorophenyl group, 3, 4, 5 monotrichlorophenyl group, 3, 4-difluorophenyl group, 3-utrophenyl group, 3-cyanophenyl group, benzothiophene 2-yl group, 3,5-difluorophenyl group, 3-trifluoromethylphenyl group, 2,4-difluorophenyl group, 3 —Methylsulfuruylphenyl group, 3,5-bis (trifluoromethyl) phenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 4-trifluoromethylphenyl group, and 3,5-bis (3 ′ , 5, bis (trifluoromethyl) phenyl) a group selected from the group consisting of phenyl groups That.

 In still another embodiment, the compound represented by the above formula (I) is represented by the following formula (I,):

(Where R ¹ and R ¹ ′ are each independently a hydrogen atom, 3, 4, 5-trifluorophenyl group, 3, 4, 5-trichlorophenyl group, 3, 4-difunoleolo, Phenyl group, 3--Trophenyl 'group, 3-Cyanophenyl group, Ben Zothiophene 2— ^ f group, 3,5-difluorophenyl group, 3-triphenylolenomethylphenyl group, 2,4 difluorophenyl group, 3-methyl 'sulfurylphenyl group, 3,5-bis ( Trifluoromethyl) phenyl group, 4 nitrophenyl group, 4 cyanophenyl group, 4 trifluoromethyl phenyl group, and 3, 5 _bis (3,, 5, 1 bis (trifluoromethyl) ) Phenyl) is a group selected from the group consisting of phenyl groups, and R ⁷ , R ⁸ and X— are each independently defined in the same manner as the compound represented by the above formula (I). Is a compound represented by the following formula:

In one embodiment, R ⁷ of the compound represented by the formula (I) is a C ₁₃ -C ₂₂ alkyl group which may form a branch or a ring.

In a further embodiment, R ⁷ and R ⁸ of the compound represented by formula (I) are the same.

In one embodiment, the compound represented by the formula (I) is used at a ratio of 0.001 mol ° / ₀ to 5 mol ·% with respect to 1 mol of the compound represented by the formula (IV). Used.

 In a further embodiment, the compound represented by the formula (I) is used at a ratio of 0.005 mol% to 0.5 mol% with respect to 1 mol of the compound represented by the formula (IV). .

 The present invention also provides a method for producing an optically active α-amino acid, the method comprising a compound represented by the formula (V I) obtained by the above method:

(Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same as defined above) and imino groups (R ¹⁴ R ¹⁵ C 2 N—) and ester groups (one C0 ₂ R ¹⁷ ) hydrolyzing under acidic conditions. The present invention also provides a method for producing an optically active single amino acid, which comprises a compound represented by the formula (VI) obtained by the above method:

(Where R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same as defined above) hydrolyze the imino group (R ¹⁴ R ¹⁵ C = N—) under acidic conditions And hydrolyzing the ester group (one CO ₂ R ¹⁷ ) of the acidic hydrolyzate under acidic or basic conditions.

 The present invention also provides a method for producing an optically active single amino acid, the method comprising a compound represented by the formula (V I) obtained by the above method:

(Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same as defined above) hydrolyzing an ester group (—C0 ₂ R ¹⁷ ) under basic conditions; And a step of hydrolyzing an imino group (R ¹⁴ R ¹⁵ C═N—) of the basic hydrolysis product under acidic conditions.

According to the present invention, a chiral phase transfer catalyst having a more simplified structure is provided. This phase transfer catalyst can be produced with fewer steps than conventional compounds. Furthermore, by including a long-chain alkyl group in the catalyst structure, a chiral phase transfer catalyst that provides high stereoselectivity in an asymmetric alkylation reaction or the like is provided. When such a phase transfer catalyst is used, it is expected that a high stereoselectivity can be obtained even in a reaction in which a conventional catalyst cannot obtain a sufficient stereoselectivity. The phase transfer catalyst of the present invention can be used, for example, in the synthesis of monoalkyl monoamino acid derivatives and α, _α -dialkyl monoamino acids. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, terms used in the present specification are defined.

 The term “an alkyl group of 0 to 0 which may form a branch or a ring” (where n is an integer) is any linear alkyl group having 1 to n carbon atoms, 3 to n carbon atoms And any cyclic alkyl group having 3 to n carbon atoms. For example, arbitrary linear alkyl groups having 1 to 6 carbon atoms include methyl, ethynole, n-propyl ', n-butyl', n-pentyl ', and n-hexyl. Arbitrary branched alkyl groups of 6 include isopropyl ', isobutyl', tert-butyl, isopentyl, etc., and optional cyclic alkyl groups of 3 to 6 carbon atoms include cycloptyl ', cyclopentyl, cyclohexyl, etc. Is mentioned. Further, for example, the term “the same alkyl group which may form a branch or a ring and may be substituted with Z or a halogen atom” is a straight chain having 1 to 12 carbon atoms. Including alkyl group, any branched chain alkyl group having 3 to 12 carbon atoms, and any cyclic alkyl group having 3 to carbon atoms: L 2 is substituted with a halogen atom at any position May be. Examples of such an alkyl group include n-heptyl ', isoheptyl, n-octyl, isooctyl, n-decyl, n-dodecyl and the like.

In N- (di-alkyl) carbamoyl group and N, N-di (C j -C ₄ alkyl) carbamoyl, “di-alkyl” is a straight-chain alkyl group of 0 to C ₄ or C ₃ means a branched-chain alkyl group -C _4.

The term “C ₂ -C _n alkenyl group which may form a branch or a ring” (where n is an integer) means any straight chain alkenyl group having 2 to n carbon atoms, 3 to n carbon atoms Any branched chain alkenyl group, and 3 to 3 carbon atoms! ! Including any cyclic alkenyl group. For example, an arbitrary straight-chain alkenyl group having 2 to 6 carbon atoms includes: etul ', 1-propenyl 2-propenore, 1-buture, 2-butene Ninore, 1-penteninole, 2-penteninole, 3-penteninole, 4-penteninole, 1-hexenyl, etc., and any branched chain alkenyl group having 3 to 6 carbon atoms includes isopropenyl, 1 —Methyl-1 monopropenyl ', 1-methyl-2 monopropenyl', 2-methyl 1-fu. L-Penyl ', 2-Methyl' 1-Propeninole, 1-Methyl-2-Butul, and the like, and any cyclic alkenyl group having 3 to 6 carbon atoms includes cyclobutyr ', cyclopent Examples include tulle and cyclohexenyl. Further, for example, the term “a C ₂ to C ₁₂ alkenyl 'group which may form a branch or a ring and / or may be substituted with a halogen atom” has 2 to 1 carbon atoms. 2 linear alkenyl groups, any branched alkenyl group having 3 to 12 carbon atoms, and any cyclic alkenyl group having 3 to 12 carbon atoms, and a hydrogen atom at any position thereof is a halogen atom May be substituted. Such alkenyl groups include 1-heptenyl, 2-heptul, 1-octul, 1-decenyl, 1-dodecenyl, and the like. '' The term “C ₂ -C _n alkynyl group which may form a branch or a ring” (where n is an integer) means any straight chain alkynyl group having 2 to n carbon atoms, 3 to 3 carbon atoms Including any branched alkynyl group of n and any cyclic alkynyl group having 3 to n carbon atoms. For example, as an arbitrary straight chain alkynyl group having 2 to 6 carbon atoms, there may be mentioned: Examples of the arbitrary branched alkynyl group having 3 to 6 include 1-methyl-2-propynyl, and examples of the optional cyclic alkynyl group having 3 to 6 carbon atoms include cyclopropyl ether and cyclobutyl ether. Can be mentioned. Further, for example, the term “a C ₂ to C ₁₂ alkynyl group which may form a branch or a ring and may be substituted with a halogen atom” has 1 to 1 carbon atoms. 2 straight-chain alkyl groups, any branched alkynyl group having 3 to 12 carbon atoms, And any cyclic alkynyl group having 3 to 12 carbon atoms, and the hydrogen atom at any position thereof may be substituted with a halogen atom. Examples of such alkynyl groups include 1-heptul, 1-octynyl, 1-decynyl, 1-dodecynyl and the like.

 'The term "an alkoxy group that may be branched ^ to the same" (where n is an integer) is an alkoxy group having an arbitrary linear alkyl group having 1 to n carbon atoms and an arbitrary one having 3 to n carbon atoms. And an alkoxy group having a branched alkyl group. Examples include methyloxy, ethyloxy, n-propyloxy, isopropyloxy, tert-butyloxy and the like.

 In the present invention, examples of the term “aralkyl group” include benzyl, phenethyl, and naphthylmethyl.

 In the present invention, examples of the term “heteroaralkyl group” include pyridylmethyl ′, indolylmethyl, furylmethyl, chenylmethyl, and pyrrolylmethyl.

 In the present invention, examples of the term “aryl group” include phenyl, naphthyl, anthryl, phenanthryl and the like.

 In the present invention, examples of the term “heteroaryl group” include pyridyl, pyrrolinole, imidazolyl, furyl, indolyl, chenyl, oxazolyl, benzothiol-2-yl, thiazolyl, and tetrazolyl.

 In the present invention, examples of the term “halogen atom” include chlorine atom, bromine atom, iodine atom and fluorine atom. In the present invention, the term “halide anion” means a halogen ion, and includes a chloride ion, a bromide ion, an iodide ion, and a fluoride ion.

In the present invention, the term “optionally forming a branched or ring, C. to C _n “Aryl group or substituted aryl group” (where n is an integer) is a aryl group, or any total number of carbon atoms having substituents at the 1 and Z or 2 and Z or 3 positions, 4 to! ! Of the substituted aryl group. For example, 2-butyr, 1-cyclopentenylmethyl, 3-methyl-2-butenyl and the like can be mentioned.

In the present invention, the term “optionally branched C ₃ -C _n propargyl group or substituted propargyl group” (where n is an integer) is a propargyl group or substituted at the 1 and / or 3 position. It means a substituted propargyl group having 4 to n total carbon atoms having a group. For example, 2-butul ', 3-trimethylsilyl-2-propynyl and the like can be mentioned.

 In the present invention, the term “functional group having a leaving ability” means an atom or an atomic group that separates from a reaction substrate in a substitution reaction or elimination reaction, that is, a leaving group. Examples thereof include a halogen atom and a sulfonyloxy group.

 In this specification, for convenience,

"CC ₄ alkyl group which may be branched and optionally substituted with a halogen atom,

Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group,

A halogen atom, which may be branched and optionally substituted with a halogen atom, a C ₁ -C ₄ alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ² and R ²¹ are each Independently a hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a force rubamoyl group, N— (Ci C alkyl) force rubamoyl group, N, N-di (Ci C alkyl) substituted with a rubamoyl group, or one NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and substituted with a halogen atom). You may have an ariel group, Ciano group,

_ _NR 20 _R 21 (wherein, R2. And R2i are each independently a hydrogen atom, or at any good C i to C ₄ alkyl group optionally substituted with C port plasminogen atoms),

 Nitoguchi,

 Force rubymoyl group,

 N- (. ^ ~ ^ Alkyl) force rubermoyl group,

 N, N-dialkyl) strong rubermoyl group,

-NHCOR ⁹ (wherein R ⁹ is a C alkyl group that may be branched and optionally substituted with a halogen atom), and

 Halogen atom

"Group consisting of" may be described as "Group (Q)".

 Hereinafter, the present invention will be described in detail.

 The quaternary ammonium salt of the present invention has the following formula (I) ′:

(Where RR ¹ ' _s R ² , R ² ', R ³ , R ³ R ⁴ , RRRR ⁶ and R ⁶ 'are each independently

 (i) a hydrogen atom;

(ii) -NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a C ₄ to C ₄ alkyl group optionally substituted with a halo atom) ; (iii) a cyano group;

 (i v) a nitro group;

 (v) force rubermoyl group;

(vi) N— (C ₁ -C ₄ alkyl) force rubamoyl group;

 (V i i) N, N-di (dialkyl) rubamoyl group;

(viii) — NHCOR ⁹ (wherein R ⁹ is a C i to C ₄ alkyl group which may be branched and optionally substituted with a halogen atom);

 (ix) an alkyl group of C Ce which may form a branch or a ring and may be substituted with a halogen atom;

(X) branched or cyclic and may be substituted or a well and Ha port Gen atom to each other to form Al 'Kenyir group c ₂ to c _6;

(X i) may form a branched or cyclic and may be substituted with a halogen atom, an alkynyl group of C ₂ -C _6;

 (X i i) aralkyl group, wherein the aryl moiety constituting the aralkyl group is

Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl 'group,

Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group,

Halogen atom, which may be branched and may be substituted with a halogen atom 〇 to 〇 Alkyl group, cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently , May be substituted with a hydrogen atom or a halogen atom, which is an alkyl group), a nitro group, a strong rubamoyl group, an N— (Ci C alkyl) carbamoyl group, an N, N—di (C ₁ ~ C ₄ alkyl) Forced rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ is a CC alkyl group which may be branched and may be substituted with a halogen atom) Optionally substituted with an aryl group,

 Ciano group,

-NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a C ₄ to C ₄ alkyl group optionally substituted with a halogen atom),

 Nitoguchi,

 Canolepamoyl group,

N- (C ₁ -C ₄ alkyl) force rubermoyl group,

N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

-NHCOR ⁹ (where, R ⁹ is branched c ₁ may be substituted in good and halogen atom have to c ₄ alkyl group), and

 Neurogen atom

An aralkyl group which may be substituted with at least one group selected from the group (Q) consisting of:

 (x i i i) a heteroaralkyl group having a heteroaryl moiety, wherein the heteroaryl moiety may be substituted with at least one group selected from the group (Q) above;

(X i V) aryl group, wherein the aryl group may be substituted with at least one group selected from the above group (Q), or the 3rd and 4th positions are joined together Optionally substituted with O— (CH ₂ ) _m —〇1 (where m is 1 or 2), an aryl group; and

 (XV) a heteroaryl group, which is optionally substituted with at least one group selected from the above group (Q);

 A group selected from the group consisting of forces,

R ⁷ and R ⁸ are each independently a monovalent organic group, and X scratch, halide Anion, S CN @ -, HS_〇 ₄ -, or HF ₂ - and the compounds represented by der Ru), preferably Ru pure compound der respect axial asymmetry. The compound represented by the above formula (I) may have any configuration of (S) or (R).

The compound represented by the formula (I) is, for example, a phase transfer catalyst for producing an optically active α-amino acid or a derivative thereof described below, in particular, an α, hedialkyl mono α-amino acid or a derivative thereof. As useful as. More specifically, the compound represented by the formula (IV) is alkylated with the compound represented by the formula (V) to produce the optically active amino acid represented by the formula (VI) or a derivative thereof. Therefore, when the compound represented by the above formula (I) is used as a phase transfer catalyst, the ammonium moiety constituting the cation of the compound:

Contributes to the reactivity in the alkylation, and the binaphthyl moiety:

Contributes to the stereoselectivity of the alkylation reaction. Therefore, in one embodiment, R ⁷ and R ⁸ in the compound represented by the formula (I) are independently derived from the ammonium moiety and the binaphthyl moiety of the cation. It is a group that can maintain reactivity and selectivity, or a group that does not inhibit the reactivity and selectivity, and has a predetermined carbon chain. For example, it is a monovalent organic group that is inert and has a predetermined number of carbon atoms as compared with the above-mentioned anmolybum moiety and binaphthyl moiety. In other words, R ⁷ and R ⁸ Are each independently a group that is not itself (or itself) rich in reactivity, and thus is a group that does not affect the reaction in the production of the amino acid or derivative thereof described below.

In the above formula (I), R ⁷ is more specifically C _{13 to} C ₃ which may form a branch or a ring. The alkyl group is preferably a C ₁₃ -C ₂₂ alkyl group which may form a branch or a ring. In R ⁷ , the lower limit of the number of carbon atoms constituting the alkyl group that may form a branch or a ring is preferably 13 or more, more preferably 15 or more, still more preferably 17 or more, and still more preferably The upper limit of the number of carbon atoms constituting the alkyl group is preferably 30 or less, more preferably 22 or less, even more preferably 21 or less, and even more preferably 20 or less. .

In the above formula (I), more specifically, R ⁸ is preferably an alkyl group of 1 to 6 which may form a branch or a ring. R ⁸ may be a branched or ring-forming alkyl group that may form a branch or a ring, or may be a branched or ring-formed c ₁₃ -c ₃₀ alkyl group (further, preferably may be branched or alkyl Le group forms a ring optionally C ₁₃ even though -C ₂₂₎ by. In the above formula (I), when R ⁸ is a C i ₂ alkyl group which may form a branch or a ring, the lower limit of the number of carbon atoms constituting the alkyl group is preferably 1 or more The upper limit of the number of carbon atoms constituting the alkyl group is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. In the above formula (I), when R ⁸ is a C _{13 to} C ₃₀ alkyl group which may form a branch or a ring, the lower limit of the number of carbon atoms constituting the alkyl group is preferably 1 or more, more preferably 15 or more, even more preferably 17 or more, and still more preferably 18 or more, and constitutes the alkyl group. The upper limit of the number of carbon atoms is preferably 30 or less, more preferably 22 or less, even more preferably 21 or less, and even more preferably 20 or less.

The number of carbon atoms constituting these alkyl groups of R ⁷ and R ⁸ can be appropriately selected according to the substrate and reactivity of the alkylation reaction.

In the present invention, in the above formula (I), RR ¹ ′, R ² , R ² ′, R ³ ,

R ³ ′, R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′, R ⁶ and R ⁶ ′ are preferably each independently

 (i) a hydrogen atom;

 (X i V) aryl group, where the aryl group is

Ci to C ₄ alkyl group which may be branched and may be substituted with a halogen atom,

Branched and may have halogen 'optionally substituted c ~ C ₅ alkoxy group atom,

A halogen atom, which may be branched and optionally substituted with a halogen atom; a Ci C alkyl group, a cyano group, an NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently , A hydrogen atom, or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl group, N- (Ci C. alkyl) a strong rubamoyl group, N, N— Di (Ci C alkyl) substituted with a strong rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and substituted with a halogen atom). It ’s good.

 Ciano group,

_{_NR} 20 _R 21 (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or an alkyl group which may be substituted with a halogen atom)

Nitro group, Force rubymoyl group,

N— (C ₁ -C ₄ alkyl) force rubamoyl group,

 N, N-di (ji ~ alkyl) force ruberamoyl group,

NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and may be substituted with a halogen atom),

 Halogen atoms and

-S (0) _n -R (where n is 0, 1 or 2 and R is a Ci to C ₄ alkyl group which may be branched and substituted with a halogen atom) is there) ;

Or may be substituted with at least one group selected from the group consisting of O— (CH ₂ ) _m -0- (where m is 1 or 2 Is)

Optionally substituted by an aryl group; and

 (XV) a heteroaryl group, wherein the heteroaryl group is

 An alkyl group which may be branched and optionally substituted with a halogen atom,

 Ci Cs alkoxy 'group, which may be branched and optionally substituted with a halogen atom,

A halogen atom, which may be branched and optionally substituted with a halogen atom, a Ci C alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently A hydrogen atom or an alkyl group which may be substituted with a halogen atom), a -tro group, a strong rubamoyl group, N— (C ₁ -C ₄ alkyl) a strong rubamoyl group, N, N— Di (C ₁ -C ₄ alkynole) force rubamoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and may be substituted with a halogen atom) ) May be substituted with an aryl group, Ciano group,

_ _NR 20 _R 2! (Wherein _R 2 and _R 2 i are each independently a hydrogen atom or a C i to C ₄ aralkyl group optionally substituted with a halogen atom) ,

 Nitro group,

 Force rubymoyl group,

 N— (〇 to. Alkyl)

N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

-NHCOR ⁹ (wherein R ⁹ is a Ci to C ₄ alkyl group which may be branched and optionally substituted with a halogen atom), and

 Halogen atom

A heteroaryl group optionally substituted with at least one group selected from the group consisting of: selected from the group consisting of: More preferably, a hydrogen atom,

3, 4, 5—Trifluoro'orophenyl group, 3, 4, 5—Trichlorophenyl group, 3, 4—Difluorophenol. 2-Nole group, 3-Nitrophenyl group, 3_Cyanophenyl group, Benzthiophene group 2-yl group, 3,5-difluorophenyl group, 3-trifluoromethylphenyl group, 2,4-difluorophenyl group, 3-methylsulfurphenyl group, 3,5-bis (trifluoromethyl) Selected from the group consisting of phenyl, 4-nitrophenyl, 4-cyanophenyl, 4-trifluoromethyl, and 3,5-bis (3,5,1bis. (Trifluoromethyl) phenyl) phenyl Is done. In particular, among the compounds represented by the above formula (I), the following formula ():

(ここで、 R¹および R¹'は、 それぞれ独立して、'水素原子、 3, 4， 5— トリフルオロフェニル基、 3, 4, 5—トリクロ口フエニル基、 3, 4—ジ フノレオロフェニル基、 3—ニトロフエ-ル基、 3—シァノフエニル基、 ベン ゾチォフエニノレー 2—ィル.基、 3, 5—ジフルオロフェニル '基、 3—トリフ ルォロメチルフエ二.ル基、 2， 4—ジフル'オロフェニル '基、 3—メチル 'スノレ ホユルフェニル '基、 3, 5—ビス （トリフルォロメチル） フエニル基、 4一 ニトロフエニル.基、 4一シァノフエ二ル基、 4一トリフルォロメチルフエ二 ル基、 および 3, 5—ビス （3， ， 5 ' 一ビス （トリフルォロメチル） フエ ニル） フエニル'基からなる群より選択される基であり、 そして R⁷、 R⁸およ ぴ X—は、 それぞれ独立して、 上で定義される基である） で表される化合物 が好ましい。

(Wherein R ¹ and R ¹ ′ are each independently a hydrogen atom, 3, 4, 5-trifluorophenyl group, 3, 4, 5-trichlorophenyl group, 3, 4-diphenolo; Lophenyl group, 3-nitrophenyl group, 3-cyanophenyl group, benzothiophenoleyl 2-yl group, 3,5-difluorophenyl 'group, 3-trifluoromethylphenyl group, 2, 4 —Difluor'orophenyl 'group, 3-Methyl'snorhoylphenyl' group, 3,5-Bis (trifluoromethyl) phenyl group, 4-Nitrophenyl group, 4-Sianophenyl group, 4-Trifluoromethylphenol And a group selected from the group consisting of 3,5-bis (3,5'-bis (trifluoromethyl) phenyl) phenyl 'groups, and R ⁷ , R ⁸ and X— is each independently a group defined above) Are preferred.

 The quaternary ammo: nimu salt represented by the above formula (I) has the following formula (I I)

(Where RR, R ² , R ² ′, R ³ , R ³ ′, R ⁴ , R ⁴ , R ⁵ , R., R ⁶ and R ⁶ ′ are defined in the above formula (I) And Z is a hydrogen atom) in the presence of an acid scavenger in an organic solvent in the following formula (III):

^HN , _D 8 (III)

Here, R ⁷ and R ⁸ can be produced by reacting with a secondary amine represented by the above formula (I). The compound of the above formula (II) can be obtained, for example, from the readily available 1,1′-binaphthyl-2,2′-dicarboxylic acid (see Seki, M. et al., Synthesis, 2000, .1677) and the following scheme 1 (See Ooi, T. et al., J. Org. Chem., 2003, 68, p. 4577). 1, 1 '_ Binaphthyl 2, 2' —dicarboxylic acid is either (S) or (R)

スキーム 1

Scheme 1

A specific description will be given based on scheme 1 above. First, dicarboxylic acid (1) is converted to the corresponding diisopropyl ester (2) using isopropyl bromide, catalysts Bu ₄ N · HS0 ₄ and KF · '2H ₂ 0. The resulting compound

(2) is treated with bis (2, 2, 6, 6-tetramethylpiperamide) magnesium (hereinafter referred to as Mg (TMP) ₂ ), and then Br ₂ is applied!] ,

3 '1 dibromo 1 1, 1, -dinaphthyl-2, 2,-dicarboxylic acid ester

Get (3). Next, in the presence of palladium acetate, triphenylphosphine, and potassium carbonate, Suzuki-Miyaura's cross-force pulling reaction of the obtained compound (3) and 3, 4, 5-trifnoreo oral phenylboronic acid was performed, 3,3 'monobis (3,4,5-trifluorophenyl) 1,1,1'-binaphthyl-2,2'-dicarboxylic acid ester (4) is obtained. Further, the alcohol (5) obtained by reducing (4) with Li A 1 H ₄ can be treated with PB r ₃ to obtain dibromide (6) corresponding to the above formula (II). it can.

 On the other hand, as the secondary amine of the above formula (I I I), either a commercially available product or a synthesized product can be used. The class II fan of the above formula (III) is, for example, according to the method described in Rajkumar Sunil Singh et al., Chemistry-A European Journal 2002, No. 8, pp.900-909. It can be readily prepared by those skilled in the art by reductive amination with min.

The organic solvent used in the step of producing the compound of the above formula (I) by reacting the compound of the above formula (II) with the compound of the above formula (II) includes nitrile solvents (for example, acetonitrile, propionitrile, etc.). Etc.), ether solvents (eg, dioxane ', tetrahydrofuran, isopropyl ether, diethyl ether, dimethoxetane, 2-methoxetyl ether), alcohol solvents (eg, methanol, ethanol, n-propanol, Sopropanol, _n -butanol, tert-butanol, etc.). In the present invention, acetonitrile is particularly preferable. Examples of the acid scavenger include inorganic bases such as potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate.

In the above reaction, the secondary amine of formula (III) is preferably used in a proportion of 0.5 to 4 equivalents, more preferably 0.8 to 2 equivalents, relative to the compound of formula (.1 I). The acid scavenger is preferably used in an amount of 1 to 4 equivalents, more preferably about 1 to 2 equivalents, relative to the compound of formula (II). The compound of formula (II) and the secondary amine of formula '(III) are reacted with stirring in a suitable organic solvent in the presence of an acid scavenger. The reaction temperature is preferably from room temperature to the boiling point of the organic solvent, and more preferably the reaction is carried out under heating and reflux. Reaction time is preferred 30 minutes to 24 hours, more preferably 6 to 12 hours. At this time, the organic solvent is preferably used in an amount of 5 to 50 times, more preferably 5 to 30 times the volume (mL) / weight (g) ratio with respect to the compound of formula (II). . After completion of the reaction, the reaction mixture can be isolated and purified by extraction with dichloromethane, dichloroethane, carbon tetrachloride, etc., silica gel force ram chromatography, etc. to obtain the compound of formula (I). Alternatively, the reaction mixture may be used as it is as a phase transfer catalyst in the method for producing an α-amino acid derivative described in detail below.

The compound of formula (I) thus obtained in which X is a halide anion is in a pure form with respect to axial asymmetry and can be used as a phase transfer catalyst. Here, “pure with respect to axial asymmetry” means that among the stereoisomers that can be considered based on axial asymmetry, the presence of one specific isomer is greater than that of the other isomers. Preferably, the abundance of the one particular isomer is 90% or more, more preferably 95% or more, even more preferably 98% or more. 'In addition, the compounds of formula (I) above X is a halide Anion, if example embodiment, through the following steps, CN @ - halide Anion is S, HS0 ₄ -, or was converted into HF ₂ one It can be a compound.

First, X is S CN or HS0 ₄ - a method for manufacturing a a a compound of formula (I).

 The compound of the formula (I) wherein X is a halide anion obtained as described above can be obtained, for example, in a suitable second organic solvent in accordance with the method described in JP-A-2002-173492. X- is converted from halide cation to SCN- by mixing with a saturated aqueous solution of alkali metal thiocyanate.

Examples of second organic solvents that can be used in this transformation are: dichloromethan. Chlorohonolem, dichloroethane, tetrahydrofuran, methinole t-petite. Examples include ruether ', diisopropyl ether', and ethyl acetate. Examples of alkali metal thiocyanate include thiocyanate strength and sodium thiocyanate.

 The reaction of the compound of formula (I) where X- is a halide anion and the alkali metal thiocyanate is mixed and contacted in solution under relatively mild conditions such as room temperature. Thus, the reaction product (that is, the compound of the formula (I) in which X is SCN) can be easily obtained in a quantitative yield.

The compounds of formula (I) above X one is SCN, by reaction with concentrated nitric acid, X- from SCN, are readily converted into further HS0 ₄ scratch. The compound of formula (I) in which X thus obtained is HS0 ₄ is further reacted with an alkali metal fluoride salt (for example, potassium fluoride, sodium fluoride or lithium fluoride). For example, it can be used as a catalyst in the reaction of silyl enol ether with a carbonyl compound (aldol reaction), which has the formula (I a):

(Where R ¹ R ¹ ′, R ² , R ² ′, R ³ , R ³ ′, R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′, R ⁶ and R ⁶ ′ are represented by the above formula (I It is also possible to obtain the compound represented by '') as defined in).

The silyl enol ether used in the above aldol reaction is, for example, a tolylalkylsilyl enol ether. Tolylalkylsilyl Enol ethers can be chlorosilanes such as trimethyl silyl chloride and triethyl silyl chloride in the presence of a carbonyl compound (eg, 2-butanone, 4-pentene-2-one ', jetyl ketone, acetophenone). It can be prepared in advance by reacting with a ketone derivative such as', propiophenone, butyronaphthone ', cycloxyhexanone', 1-oxoindane, 1-tetralone, or 2-tetralone.

 Examples of the carbonyl compound that reacts with the silylenol ether used in the above-mentioned aldol reaction include a carbonyl compound (the above ketone derivative) that is a precursor of silyl enol ether, acetyl aldehyde, propion aldehyde, butyl aldehyde, Isobutyl aldehyde, Isobarrel aldehyde,-Force Pron aldehyde, Dodecyl aldehyde, + Palmitic aldehyde, Stear aldehyde, Acrolein, Croton aldehyde, Sick mouth Xanthan aldehyde, Benz aldehyde, Annis aldehyde, Nicotine aldehyde Examples include aldehyde compounds such as namaldehyde, ct-naphthoaldehyde, and β-naphthoaldehyde.

 With respect to such silyl enol ether and carbonyl compound, the compound represented by the formula (I a) is used as a catalyst for the aldol 'reaction, and the stereoselectivity of the reaction can be controlled.

Next, a method for producing the compound of the formula (I) in which X— is HF ₂ will be described. The compound of formula (I) wherein X— obtained as described above is a halide anion is first contacted with an ion exchange resin to produce a first intermediate. Any ion exchange resin can be selected by those skilled in the art. Specific examples of ion exchange resins that can be used include Amberlyst A 2 6 (OH) (manufactured by Organo Corporation).

Contact of a compound of formula (I) where X— is a halide anion with an ion exchange resin can be achieved, for example, by a compound of formula (I) wherein X— is a halide anion. This is done by dissolving the product in a suitable third solvent and passing this solution through a column packed with the ion exchange resin. The third solvent that can be used in performing such contact is preferably an alcohol solvent. Specific examples of the alcohol solvent include, but are not limited to, methyl alcohol, ethyl alcohol, isopropyl alcohol, and normal propyl alcohol.

 The amount of the compound of the formula (I) in which the above X is a halide anion used in this contact and the amount of the third solvent are not particularly limited and can be appropriately set by those skilled in the art.

 In this way, the first intermediate is produced.

The resulting first intermediate is then neutralized with an aqueous hydrogen fluoride solution, preferably without removing the solvent. -The amount of the hydrogen fluoride aqueous solution used in the present invention is not particularly limited, but is preferably a compound of the formula (I) wherein X is a halide anion from the viewpoint of increasing productivity. On the other hand, it is selected so that an equal amount or more of hydrogen fluoride reacts. This neutralizes the first intermediate, and in the solution X is converted from the halide ayuon to HF ₂ _ (lb):

で表される化合物を沈殿させることができる。

Can be precipitated.

Thereafter, the compound represented by the formula (lb) can be easily isolated by removing the solvent using a means commonly used by those skilled in the art. The compound represented by the formula (lb) thus obtained can be used, for example, as a catalyst for producing a diastereoselective and enantioselectively controlled nitro alcohol.

 Next, a method for producing a ct-amino acid derivative using the quaternary ammonium compound of the present invention represented by the formula (I) as a phase transfer catalyst will be described. One amino acid derivative represented by the formula (VI):

(Where R ¹⁴ and R ¹⁵ are each independently ..

 (i) a hydrogen atom; or

 (i i) an aryl group, the aryl group

 An alkyl group which may be branched and optionally substituted with a halogen atom,

Ci C ₅ alkoxy group which may be branched and may be substituted with a halogen atom,

Halogen atom, which may be branched and may be substituted with a halogen atom Yes to Yes ₄ Alkyl group, cyano group, one NR ³⁰ R ³¹ (where R ³⁰ and R ³¹ are each independently A hydrogen atom or an alkyl group optionally substituted with a halogen atom), a nitro group, a carbamoyl group,

N— (di-alkyl) Carpamoyl group, · N, N-di (di-alkyl) carpamoyl group, or one NHCOR ⁹ (where R ⁹ may be branched and substituted with a halogen atom) An optionally substituted C ₁ -C ₄ alkyl group), an aryl group,

Ciano group, NR ³⁰ R ³¹ (wherein R ³⁰ and R ³¹ are each independently a hydrogen atom or a Ci Ca alkyl group optionally substituted with a halogen atom),

 Nitro group,

 Force rubymoyl group,

N- (C ₁ -C ₄ alkyl) force rubermoyl group,

N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group,

-NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and optionally substituted with a halogen atom), and

 Halogen atom

An aryl group optionally substituted with at least one group selected from the group consisting of:

With the proviso unless R ¹⁴ and R ¹⁵ are both hydrogen atoms, R ¹⁶ is'

 (i) a hydrogen atom;

 (i i) It may form a branch or a ring and may be substituted with a halogen atom. ~ Ji. Wherein the alkyl group is

Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group,

 Ciano group,

-NR ³⁰ R ³¹ (wherein R ³⁰ and R ³¹ are each independently a hydrogen atom or a C ₄ to C ₄ alkyl group optionally substituted with a haguchi atom),

 Nitro group,

 Force rubymoyl group,

N- (C ₁ -C ₄ alkyl) force rubermoyl group, N, N—di (Ci C alkyl ') force rubermoyl group,

-NHCOR ⁹ (wherein R ⁹ 'is an alkyl group which may be branched and may be substituted with a halogen atom),

 Halogen atoms,

-COR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and optionally substituted with a halogen atom), and

C0 ₂ R ⁹ (wherein R ⁹ is a C _{1 to} C ₄ alkyl group which may be branched and may be substituted with a halogen atom)

An alkyl group optionally substituted with at least one group selected from the group consisting of:

(Ii .i) may form a branched or cyclic and may be substituted with a halogen atom, an alkenyl group of C ₂ -C _6;

(Iv) may form a branched or cyclic and may be substituted with a halogen atom, an alkynyl group of C ₂ -C _6;

 (V) an aralkyl group, wherein the aryl moiety constituting the aralkyl group may be branched and may be substituted with a halogen atom;

Ci C ₅ alkoxy group which may be branched and may be substituted with a halogen atom,

A halogen atom, which may be branched and optionally substituted with a halogen atom, a Ci C alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently A hydrogen atom or an optionally substituted alkyl group), a nitro group, a rubamoyl group,

N- (CC alkyl) force rubamoyl group, N, N-dialkylol) force rubamoyl group, or one NHCOR ⁹ (where R ⁹ may be branched and substituted with a halogen atom CC An alkyl group) Optionally substituted with an aryl group,

 Ciano group,

_{_NR} 20 _R 21 (wherein R 20 and _R 21 are each independently a hydrogen atom or an alkyl group which may be substituted with a halogen atom)

 Group

 Force rubymoyl group,

 N- (ji-ji alkyl) carpamoyl group,

 N, N—di (C C alkyl) force rubermoyl group,

-NHCOR ⁹ (where R ⁹ is a branched and optionally substituted with halogen 'atom ~ ^ alkyl group), and

 Neurogen atom

May be substituted with at least one group selected from the group consisting of (Q), and the alkyl moiety constituting the aralkyl group may form a branch or a ring and be substituted with a halogen atom. An aralkyl group which may be a C ₁ -C ₆ alkyl group;

 (v i) a heteroaralkyl group having a heteroaryl moiety, wherein the heteroaryl moiety may be substituted with at least one group selected from the above group (Q);

 (V i i) aryl group, the aryl group optionally substituted with at least one group selected from the group (Q) above; and

(V i i i) a heteroaryl group, which may be substituted with at least one group selected from the above group (Q);

 A group selected from the group consisting of:

R ¹⁷ may form a branch or a ring and is substituted with a halogen atom. C _{1 to} c ₈ alkyl group,

R ¹⁸ is

 (i) A ring or a ring may be formed and may be substituted with a halogen atom. Wherein the alkyl group is.

 A C Cs alkoxy group which may be branched and may be substituted with a halogen atom,

 Ciano group, '

_{_NR} 30 _R 31 (wherein R ³ ° and R 31 are each independently a hydrogen atom or a Ci to C ₄ alkyl group optionally substituted with a haguchi atom),

 Nito P group,

 Force rubymoyl group,

 N- (. ^ ~. Al'kill) Carbamoyl group,

 N, N—di (Ci C alkyl ') force rubermoyl group,

-NHCOR ⁹ '(wherein R ⁹ is a c ₁ -c ₄ alkyl group which may be branched and may be substituted with a halogen atom),

 Neurogen atom

-COR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and

— CO ₂ R ⁹ (wherein R ⁹ is a C ₁ -C ₄ alkyl group which may be branched and optionally substituted with a halogen atom)

An alkyl group optionally substituted with at least one group selected from the group consisting of:

(Ii) may form a branched or cyclic and may be substituted with a halogen atom, Ariru or substituted Ariru group c ₃ to c _9;

(iii) may be branched or ring and substituted with a halogen atom An alkenyl group of c _{2 to} c ₆ , which may be

(I V) to form a branched or ring may be substituted in good and halogen atom, an alkynyl group of C ₂ -C _6;

 (V) an aralkyl group, the aralkyl partial force constituting the aralkyl group, which may be substituted with at least one group selected from the above group (Q);

 (v i) a heteroaralkyl group having a heteroaryl moiety, wherein the heteroaryl moiety may be substituted with at least one group selected from the group (Q) above; and

 (V i i) may be branched and substituted with a halogen atom,

Propargyl group or substituted propargyl group C ₃ ~ C _9;

 A group selected from the group of forces, and

 (* Indicates a newly generated asymmetric center)

Compound represented by formula (IV):

(Where R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are the same as defined in formula (VI) above)

 Using a compound represented by the above formula (I) (preferably an optically active compound represented by the above formula (I)) as a phase transfer catalyst in the presence of an inorganic base in a medium. Compound (V):

R ¹⁸ -W (V)

(Wherein R ¹⁸ is the same as defined in the above formula (VI), and W is a functional group having a leaving ability). be able to. The media used in the above alkylation process include benzene, toluene, xylene, ethyl ether, isopropyl ether, tetrahydrofuran ', dioxane', mesitylene, ethyl acetate, isopropyl acetate, cyclopentyl methyl ether ', methyl tertiary butyl ether. Etc. Alternatively, the medium may be a two-phase medium of water and a medium that does not mix with water. The medium may be preferably used in a volume (mL) / weight (g) ratio of 0.5 to 30 times, more preferably 1 to 25 times with respect to the compound of formula (IV).

 Examples of the inorganic base used in the alkylation step include lithium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, rubidium hydroxide, and cesium hydroxide. The inorganic base can be used in an amount of preferably 0.5 equivalents to 100 equivalents, more preferably 0.8 equivalents to 40 equivalents, relative to the compound of formula (IV).

 In the alkylation step, the inorganic base may be used in the form of an aqueous inorganic base solution. When used in the form of an inorganic base aqueous solution, the inorganic base in the inorganic base permanent solution can be used in an amount of preferably 0.5 equivalents or more, more preferably 0.8 equivalents or more, relative to the compound of the formula (IV). The aqueous inorganic base solution is preferably 20 wZw% to 70 w / w%, more preferably 30 w / w% to 60 wZwG / o.

 The volume ratio of the medium and the aqueous inorganic base solution is preferably the ratio of the volume of the medium (mL) to the volume of the aqueous inorganic base solution (mL), preferably 7-1: LZ5, more preferably 4-1 1-11.

In the alkylation step, the compound of formula (V) is preferably used in a proportion of 0.5 to 10 equivalents, more preferably 0.8 to 5 equivalents, relative to the compound of formula (IV). Compounds of formula (I) is 1 mole of the compound of Formula (IV), preferably 0.001 mol _^0/0 or more, more preferably 0.005 mol% or more It is used as a phase transfer catalyst at the upper limit and preferably at the upper limit of 10 mol% or less, more preferably 5 mol% or less, and even more preferably 0.5 mol% or less. Thus, since the phase transfer catalyst used in the present invention has a very high catalytic activity, the desired optical activity can be obtained by using only a very small amount of the catalyst per 1 mol of the compound of the formula (IV). Nahiichi amino acid and its derivatives can be obtained.

In the present invention, an asymmetric phase-transfer catalyst represented by the formula (I) and an achiral quaternary ammonium salt such as tetraptylammonium promide (TBAB) may be used in combination. For example, TBAB functions as a co-catalyst in the reaction system of the present invention, improves the yield of the resulting α-amino acid and derivatives thereof, and is asymmetric represented by the formula (I) used in the present invention. The amount of the phase transfer catalyst can be further reduced. The amount of TBAB that can be used in the present invention is preferably 0.005 mole ⁰ / mole per mole of the compound of the above formula (IV). ~ It is 1 mole _^0/0, more preferably 0.01% - 0.8 mol _^0/0.

 The alkylation step is also performed at a suitable temperature between _70 ° C. and room temperature, preferably from 20 ° C. to 20 ° C., in air, preferably under an argon atmosphere. This step can be carried out with stirring for an appropriate time until the alkylation reaction has proceeded sufficiently. The reaction time is preferably 30 minutes to 48 hours, more preferably 1 hour to 24 hours.

 According to the method of the present invention using the compound of the formula (I) of the present invention as described above, the optically active compound of the formula (VI) can be obtained in high yield and high optical purity. Here, the high optical purity is preferably an optical purity of 80% ee or higher, more preferably 85% ee or higher, even more preferably 90% ee or higher, and even more preferably 95% ee or higher. Say.

In another aspect of the present invention, the present invention provides a method for producing an optically active α-amino acid. provide.

 That is, in the present invention, for example, one of the following procedures is performed using the compound (optically active α-amino acid derivative) represented by the optically active formula (VI) obtained by the above method. Thus, an optically active α-amino acid can be produced.

In the first method, firstly, the compound of the above obtained optically active formula by the method (VI) (optically active Nahi single amino acid derivative) constituting Imino groups ^{(RMR 1 5 C = N -} ) moiety acidic Hydrolyzed under certain conditions (imine acid hydrolysis process). Examples of acids used in the acid hydrolysis step of imine include inorganic acids (for example, hydrochloric acid, phosphoric acid, sulfuric acid) and organic acids (for example, acetic acid, citrate, p-toluenesulfonic acid). Specifically, the acid hydrolysis step of the imine is carried out by using a compound of the formula (VI) in an appropriate medium (eg, tetrahydrofuran, toluene, ethanol ', or a combination thereof) and an aqueous solution of the above acid. Proceed by using and treating at an appropriate temperature (eg, room temperature). As a result, an ester derivative of an amino acid having a terminal amino group released as an acidic hydrolysis product can be obtained.

Next, the ester derivative (acid hydrolysis product) of the amino acid obtained in the above step is subjected to a hydrolysis reaction under acidic conditions or basic conditions stronger than the hydrolysis of imine, if necessary. Thereby, the target amino acid in which the terminal of the acidic hydrolyzate (that is, the ester group (one C 0 ₂ R ^{1 7} ) constituting the acidic hydrolyzate) becomes a carboxylic acid can be obtained.

Alternatively, in the second method, steps reverse to the above are employed. In other words, the ester group (one C 0 ₂ R ¹⁷ ) constituting the optically active compound of formula '(VI) (optically active α-amino acid derivative) obtained by the above alkylation reaction is converted to basic First hydrolyze under conditions (basic ester hydrolysis step). In the basic hydrolysis step of this ester, a sodium hydroxide aqueous solution or the like An aqueous solution of Lucari can be used. By performing such hydrolysis, the formula

A basic hydrolysis product in which the terminal of the compound (VI) (that is, the ester group (—C0 ₂ R ¹⁷ ) constituting the compound of the formula (VI)) is a carboxylic acid can be obtained.

Next, the imino group (R ¹⁴ R ¹⁵ C =

N-) Hydrolyze the part under acidic conditions (acid hydrolysis step of imine). Examples of acids used in the acid hydrolysis step of this imine include inorganic acids (eg, hydrochloric acid, phosphoric acid, sulfuric acid) or organic acids (eg, acetic acid, citrate, p-toluenesulfonic acid). . Specifically, the acid hydrolysis step of the imine is carried out by using the basic hydrolyzate in an appropriate medium (for example, tetrahydrofuran, toluene, ethanol, or a combination thereof) using an aqueous solution of the acid. Proceed by processing at an appropriate temperature (eg, room temperature). As a result, the target amino acid from which the terminal amino group has been released can be obtained. In the present invention, when the amino acid is produced from the compound of the formula (VI), either the first method or the second method described above may be used, and the specific structure of the amino acid actually produced Further, it can be arbitrarily selected by those skilled in the art according to other manufacturing conditions.

Example

 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

 In the following examples, the NMR spectrum is defined as JEOL JNM-FX.

Measured with a 400 (400MHz) spectrometer, JMTC-400 / 54 / SS (400MHz) spectrometer, or AVANCE-400 (400MHz) spectrometer from Bruker Biospin. The MS spectrum was measured with HITACHI M-8000. The optical purity of the reaction product can be determined by high performance liquid chromatography (HPLC) 4.6 ram X 25cra Daicel Chiralcel 0D, 0D_H, AD, or AD-H, measured with Shimadzu 10 instrument and Waters 2690. The progress of the reaction was monitored using thin layer chromatography [Merck precoated TLC plate (silica gel 60 GF254, 0.25 mm)]. Reference Example 1: Synthesis of starting material (compound 6) for the synthesis of quaternary ammonium salt>

スキーム 1

Scheme 1

Compound 1 (S form), Compound 1 against 10 equivalents of isopropyl bromide, 20 mo 1% of Catalyst B u ₄ N · Η≤0 _4, and 10 equivalent fluoride. Potassium 2 hydrate thereof, Tetorahi The reaction was carried out under reflux in drofuran for 24 hours to obtain Compound 2 in a yield of 95%. To this compound 2, add 4 equivalents of Mg (TMP) ₂ freshly prepared in tetrahydrofuran. C. Then, 8 equivalents of bromine were added dropwise at 178.degree. C., and then stirred at room temperature for 1 hour to obtain Compound 3 in a yield of 91%. Compound 3 was prepared in the presence of 5m o 1% palladium acetate, 15m o 1% PP h ₃ in dimethylformamide, and 3 equivalents of potassium carbonate. A Suzuki-Miyaura cross-force coupling reaction with 3,4,5-trifluorophenylpo-noic acid was carried out at 90 ° C. for 8 hours to obtain Compound 4 in 94% yield. Compound 4 was then reduced with 3 equivalents of Li A 1 H ₄ in tetrahydrofuran at 0 ° C. to room temperature, and the resulting compound 5 was then converted to 0.5 equivalents of PB in tetrahydrofuran at 0 ° C. After stirring for ₃ hours with r ₃ , compound 6 (S form) was obtained with a yield of 90%. The R form was also prepared by the same procedure.

<Reference Example 2: Synthesis of quaternary ammonium salt (compound 7)>

 (6) (7) Compound 6 (S form) (28 Omg, 0.4 mmo 1), dibutylamine (140 / z L, 0.8 mmole) obtained in Reference Example 1 in acetonitrile (5 mL) And a mixture of potassium carbonate (82 mg, 0.6 mmo 1) were heated to reflux with stirring for 10 hours. The resulting mixture was poured into water and extracted with dichloromethane. The organic layer extract was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (eluent: methanol Z dichloromethane = 1: 20) to obtain compound 7 (S form) (247 mg, 0.33 mmol 1) in 83% yield.

Table 1 shows the NMR spectrum of the obtained compound 7 (S form). table 1

 NMR spectrum of Compound 7 (S form) obtained above

¹ H NMR (400 Hz, CDCI ₃ ) 57.97-7.95 (4H, m, Ar-H), 7.55- 7.51 (2H, m, Ar-H), 7.27-7.23 (8H, m, Ar-H), 4.99 (2H, d, J

= 14.2Hz, Ar-CH ₂ ), 3.74 (2H, d, = 13.9Hz, Ar-CH ₂ ), 3.32 (2 H, t, J = 12.5Hz, N—CH ₂ — CH ₂ ), 2.56 (2H , t, J = 12.3Hz, N-CH ₂ | -CH ₂ ), 1.06-0.97 (6H, m, CH ₂ ), 0.71 (6H, t, J = 6.9Hz, CH ₃ ) 0.23 (2H, bs, CH ₂ ); ¹³ C NMR (100 MHz, CDCI ₃ ) (5150.95 (d, J _{c →}

, 115.31 -113.76(m), 57. = 253Hz), 13 15, 15Hz), 138.31, 136.8 6, 134.64 (d, 131.13, 130.85, 128.31, 128.28, 127

, 115.31 -113.76 (m), 57.

 58, 57.37, 24.60, 19.32, 13.24. The same procedure was performed for the R form of Compound 6 to obtain Compound 7 (R form).

<Example 1: Synthesis of quaternary ammonium salt (compound 8)>

まず、 Rajkuraar Sunil Singhら、 Chemistry- A European Journal, 2002年， 第 8号， pp.900 - 909に記載の方法に準じて、 対応するアルデヒドとァミンと の還元的ァミノ化により （n-C₂₀H₄₁) ₂NHを調製した。

First, according to the method described in Rajkuraar Sunil Singh et al., Chemistry-A European Journal, 2002, No. 8, pp.900-909, by reductive amination of the corresponding aldehyde and amin (nC ₂₀ H _{41 2} NH was prepared.

Next, compound 6 (S form) (105 mg, 0.15 mmo 1), (nC ₂₀ H ₄₁ ) ₂ NH (8 6.7 mg, 0.15 mm) obtained in Reference Example 1 in acetonitrile (5 mL) o 1) and carbonated potassium (24.9 mg, 0.

The mixture of 18 mmo 1) was heated to reflux with stirring for 10 hours. Obtained The mixture was poured into water and extracted with dichloromethane. The organic layer extract was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (eluent: methanol-dichloromethane = 1: 10), and compound 8 (S form) (158.5 mg, 0.13 mm o I) was converted to 8 Obtained in 8% yield.

 Table 2 shows the NMR spectrum 'of the obtained compound 8 (S form).

 Table 2

<Example 2: quaternary ammonium salt (compound 9)>

 (6) (9)

According to the method described in Rajkumar Sunil Singh et al., Chemistry-A European Journal, 2002: No. 8, pp.900-909, by the reductive amination of the corresponding aldehyde with amishi (n—C ₂₂ H ₄₅ ) ₂ NH was prepared.

 Next, the compound 6 obtained in Reference Example 1 in acetonitrile (10 mL) was used.

(S form) (2 10mg, 0.30 mm o 1), (n— C ₂₂ H _4S ) ₂ NH (1 A mixture of 90.3 mg, 0.3 Ommo 1), and potassium carbonate (49.8 mg, 0.36 mmo 1) was heated to reflux with stirring for 10 hours. The resulting mixture was poured into water and extracted with black mouth form. The organic layer extract was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (eluent: methanol / chloroform = 1: 10), and compound 9 (S form) (244 mg, 0.19 mm o 1) was dissolved in 65% Obtained in yield.

 Table 3 shows the NMR spectrum of the obtained compound 9 (S form).

 Table 3

化合物 6の R体についても、 同様の手順を行い、 化合物 9 (R体） を得た。

The same procedure was performed for the R form of Compound 6 to obtain Compound 9 (R form).

<Example 3-1: Preparation of the novel compounds _{10> M rn \ run u KIU} MgS0 4 NaBH 4, nC 4 9 CH 3 (CH 2) 20 c nO + nC 4 H 9 NH 2 ^ 4> HN '4 s

A CHCI ₃ MeOH, "-C ₂₂ H ₄₅

0 ° C-rt 0 ° C-rt ₍₁₀₎

 84% In order to synthesize compound 11 described later, first, novel compound 10 was prepared according to the method described in Rajkumar Sunil Singh et al., Chemistry-A European Journal, 2002, No. 8, pp.900-909. It was prepared as follows.

N-docosanal A (324. 6 mg, 1. Ommo l), n-butyramine (73. lmg, 1. Ommo 1), and black mouth form under nitrogen atmosphere 0 mixture of (3 OmL). After cooling to C, magnesium sulfate (145 mg, 1.2 mmo 1) was added at 0 ° C. The mixture was stirred for 6 hours at room temperature, filtered, and washed with methanol (3 mL × 2). The filtrate was cooled to 0 ° C and sodium borohydride (76 mg, 2. Ommol) was added at 0 ° C. After stirring at room temperature for 4 hours, black mouth form (2 OmL) was added and washed with water (25 mLX3). Further, the extract was dried over sodium sulfate and concentrated under reduced pressure to obtain Compound 10 (320 mg) in a yield of 84%. '

 Table 4 shows the NMR spectrum and MS spectrum of the obtained compound 10.

 Table 4

ァセトニトリル （10mL) 中の、 参考例 1で得られた化合物 6 (R体） ( 210 m g , 0. 30 mm o 1 ) 、 ィ匕合物 10 (1 14. 5m g， 0. 3 Ommo 1 ) 、 および炭酸力リウム （49. 8mg, 0. 36mmo 1 ) の 混合物を、 攪拌しながら 10時間加熱還流した。 得られた混合物を水中に注 ぎ、 そしてクロロホルムで抽出した。 有機層抽出物を硫酸ナトリゥム上で乾 燥させ、 そして濃縮した。 残渣を、 シリカゲルカラムクロマトグラフィー

Compound 6 (R form) obtained in Reference Example 1 (210 mg, 0.30 mm o 1), Compound 10 (1 14.5 mg, 0.3 Ommo 1) in acetonitrile (10 mL) , And carbonated lithium (49.8 mg, 0.36 mmo 1) The mixture was heated to reflux with stirring for 10 hours. The resulting mixture was poured into water and extracted with chloroform. The organic layer extract was dried over sodium sulfate and concentrated. The residue is chromatographed on silica gel column.

(Eluent: methanol / toluene = 2: 5) and purified to obtain Compound 1 1 (R form) (200 mg, 0.2 Ommo 1) in a yield of 67%.

 Table 5 shows the NMR spectrum of the obtained Compound 11 (R-form).

 Table 5

<Comparative Example 1: Alky of Compound 1 2 and Bromoacetate 'Using Compound 7

 50% KOH aqueous solution

 (12) (13)

 Glycine tert-butyl ester benzophenone Schiff base (compound 1

2) (88.6mg, 0.3mmol), Compound 7 (S Body; (S) — 7 may be used in this specification) (0.003M) Dichloromethane solution (0.05 mL, 0.15 πιο 1), 50% hydroxylation power Aqueous solution (1. OmL) and toluene (1. OmL) were mixed, and tert-butyl ester butyl acetate (70.2 mg, 0.36 mm o 1) was added under argon atmosphere. The solution was added dropwise at ° C. After stirring at 0 ° C for 16 hours, the reaction mixture was poured into water and extracted with ether. The ether extract was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The oily residue was subjected to silica gel column chromatography (eluted with ether Z hexane = 1/10) to obtain Compound 13 (10 2 mg) in 72% yield, 68% ee (R form). The optical purity of the obtained product was analyzed by HP LC [Daicel Chiralcel 0D_H; eluent: hexane Z2—propanol = 100: 1, 1. OmLZ min, 254 nm; retention time: (S) = 6.3 minutes, (R) body = 6.9 minutes]. · '

<Example 4: Compound 12 using Compound 8 and alkyl of bromoacetate

 (8)

Glycine tert-butyl ester benzophenone Schiff base (compound 1 2) (88. 6 mg, 0.3 mmol), Compound 8 obtained in Example 1 (S form; sometimes referred to as (S) — 8 in this specification) (0.003M) Di Mix chloromethane solution (0. lmL, 0.3 μmo 1), 50% aqueous potassium hydroxide solution (1. OmL), and toluene (1. OmL). 2 mg, 0.36 mm o 1) was added dropwise at 0 ° C under an argon atmosphere. After stirring at 0 ° C for 4 hours, the reaction mixture was poured into water and extracted with 'ether. The ether extract was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The oily residue was subjected to silica gel column chromatography (eluted with ether hexane = 1/10) to obtain Compound 13 (128 mg) in 91% yield, 99% ee (R form). Thus, when Compound 8 was used as a catalyst, the optical purity of the obtained product was greatly improved.

<Example 5: Alkyl of Compound 12 and Bromoacetate using Compound 9

 0)

Glycine tert-butyl ester benzophenone Schiff base (Compound 1 2) (88. 6 mg, 0.3 mmo 1), Compound 9 (S Body; (S) — 9 may be used in this specification) (0.0 0 3M) Dichloromethane solution (0.1 mL, 0.3 μηη1), 50% Aqueous power lithium hydroxide (1. OmL) and toluene (1. OmL) were mixed, and bromoacetic acid tert-butyl ester '(7 0.2 mg, 0.36 mmo 1) was added under argon atmosphere. The solution was added dropwise at 0 ° C. After stirring at 0 ° C for 4 hours, the reaction mixture was poured into water and extracted with ether. The ether extract was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The oily residue was subjected to silica gel column chromatography (eluted with ether / hexane == 1/10) to give compound 13 (10 6 mg) in 75% yield, 84% ee (R form). Got in.

<Example 6: Compound 1 2 using Compound 1 1 and bromoacetate ester

グリシン t e r t—ブチルエステルベンゾフエノンシッフ塩基 （化合物 1 2) (8 8. 6 m g , 0. 3 mm o l ) 、 実施例 1で得られた化合物 '（ 1 1 ) (R体；本明細書中にて （R) — 1 1と表記することもある） （0. 0 0 3M) ジクロロメタン溶液 （0. l mL， 0. 3 / m o 1 ) , 5 0 %水酸 化カリウム水溶液 （1. OmL) 、 およびトルエン （1. OmL) を混合し て、 ブロモ酢酸 t _{e r} t—ブチノレエステノレ （ 7 0. 2 m g , 0. 3 6 mm o

Glycine tert-butyl ester benzophenone Schiff base (Compound 1 2) (88.6 mg, 0.3 mm ol), Compound '(1 1) obtained in Example 1 (R form; in this specification) (R) — 1 1 (may be written as 1) (0. 0 0 3M) Dichloromethane solution (0. l mL, 0.3 / mo 1), 50% potassium hydroxide aqueous solution (1. OmL ), And toluene (1. OmL) Bromoacetic acid _ter t-butinoleestenole (7 0.2 mg, 0.3 6 mm o

I) was added dropwise at 0 ° C under an argon atmosphere. After stirring at 0 ° C for 4 hours, the reaction mixture was poured into water and extracted with ether. The oily residue was subjected to silica gel column chromatography (eluting with ether / hexane = 1/10) to give compound 1 3 (10 2 mg) in 7 2% yield, 7 2% ee (S body).

 When the results of Examples 4 to 6 were compared with the results of Comparative Example 1, the catalyst containing a long-chain alkyl group (compounds 8, 9 and 2 obtained in Examples 1, 2 and 3-2)

It can be seen that I I) can carry out a mono-substituted alkylation reaction with high stereoselectivity as compared with the conventional catalyst (that is, compound 7 used in Comparative Example 1). Comparative Example 2: Alalanine ester derivative 14 using compound 7

L—ァラニンェチルエステ.ルの p—クロロべンズアル'デヒ ドとのシッフ塩 基 14 (1. 20 g, 5 mm 0 1 ) , 参考例 2で得られた化合物 7 (R 体；本明細書中にて （R) — 7と表記することもある） （3. 7mg, 5 μ mo 1 ) 、 p—クロ口ベンジルブ口ミ ド （ 1. 23 g , 6 mmひ 1 ) 、 およ びトルエン （20mL) を混合して、 48%水酸化カリウム水溶液 （8. 8 8 g) を 0°Cにて滴下した。 0°Cにて 4時間攪拌した後、 反応混合物に水

Schiff salt of L-alaninethyl ester with p-chlorobensaldehyde 14 (1.20 g, 5 mm 0 1), compound 7 obtained in Reference Example 2 (R form; In this specification, (R) — 7 may be indicated) (3.7 mg, 5 μmo 1), p-black benzyl bromide (1.23 g, 6 mm 1), Then, toluene (20 mL) was mixed, and 48% aqueous potassium hydroxide solution (8.88 g) was added dropwise at 0 ° C. After stirring at 0 ° C for 4 hours, the reaction mixture was mixed with water.

After pouring (5 mL) and separating the toluene layer, the alkylated Schiff base 16 was further extracted with toluene (5 mL × 2). This was combined with the recovered toluene layer, 1N hydrochloric acid was further added, and the mixture was stirred at room temperature for 3.5 hours. After recovering the aqueous layer by liquid separation, wash the aqueous layer with toluene (10 mL), pay attention to foaming, and add sodium carbonate until the solution is pH 11 or higher (confirmed with universal pH test paper). The Schiff base 16 was extracted with ethyl acetate (20 mLX 2). The ethyl acetate layer is dried over sodium sulfate and concentrated under reduced pressure.

(S) —Hydroxymethyl-4-chlorophenylalanine ester 16. (0.61 g) was obtained with a yield of 51% and an optical purity of 90% ee.

 The optical purity of the obtained product was analyzed by HP LC [Daicel Chiralcel

AD; Eluent: Hexane Z 2 -Propanol Jetylamine = 100: 1: 0.1, 0. SmLZ min, 230 nm; Retention time: (R) body = 30 min,

(S) Body = 41 minutes].

<Example 7: Alkyrin ester derivative 14 using alkyl 9 or 11>

Schiff salt of L-alanine ethyl ester with p-black benzene aldehyde 15 (1.20 g, 5 mmol), (R)-9 (6.3 mg) obtained in Example 2 5 / zmol), p-black benzene repromide (1.23 g, 6 mm o 1), and toluene (20 mL) were mixed, and 48% aqueous potassium hydroxide solution (8.88 g) was added to 0 The solution was added dropwise at ° C. After stirring at 0 ° C. for 4 hours, water (5 mL) was added to the reaction mixture, the toluene layer was separated, and then the alkyl'-modified Schiff base 15 was extracted with toluene (5 mL × 2). This was combined with the collected toluene layer, 1N hydrochloric acid was further added, and the mixture was stirred at room temperature for 3.5 hours. After collecting the aqueous layer by liquid separation, wash the aqueous layer with toluene (10 mL). Clean and foam carefully, add sodium carbonate until solution is pH 11 or higher (confirmed with universal pH test paper) and extract compound 16 with ethyl acetate (20 mL X 2) . The ethyl acetate layer was dried over sodium sulfate and concentrated under reduced pressure to give (S) —Hi-methyl 1- 4-phenyl lanalanine ester 1 6 (0.5 5 g) in a yield of 4 Obtained at 5%, optical purity 9 2% ee.

In addition, a Schiff base 14 (1.20 g, 5 mm o 1) with L-alanine ethyl ester p-chlorobens aldehyde was used instead of (R) -9. Using (R) — 1 1 (5. Omg, 5 μ ΐη ο 1) obtained in Example 3-2, the reaction was carried out in the same manner for 4 hours, and (S) — _α —methyl _4-chlorophenylalanine Ethyl ester 16 was obtained with a yield of 45% and an optical purity of 93% ee.

 When the results of Example 7 and the results of Comparative Example 2 were compared, the catalyst containing a long-chain alkyl group (compounds 9 and 11 obtained in Examples 2 and 3-2) was a conventional catalyst (ie, Compared with the compound 7) ′ used in Comparative Example 2, it is possible to carry out a disubstituted alkylation reaction with the same or higher stereoselectivity. Industrial applicability

According to the present invention, a chiral phase transfer catalyst having a simpler structure is provided. This phase transfer catalyst can be produced with fewer steps than conventional compounds, which also reduces costs. Furthermore, a chiral phase transfer catalyst that provides high stereoselectivity in an asymmetric alkylation reaction by including a long-chain alkyl group in the catalyst structure is provided. When this phase transfer catalyst is used, it is expected that high stereoselectivity can be obtained even in a reaction in which sufficient stereoselectivity cannot be obtained with conventional catalysts. Such phase transfer catalysts include α-alkyl mono α-amino acids and derivatives thereof, and It is very useful for the synthesis of one amino acid and its derivatives. Thus synthesized. Amino acids and their derivatives are useful in the design of peptides with enhanced properties and as effective enzyme inhibitors. It also plays a special role as a chiral construct block for the synthesis of compounds with various biological activities. Therefore, it is useful for the development of new foods and pharmaceuticals.

Claims

The scope of the claims A compound represented by the following formula (I)

here, R \ R ^1- , R ² , R ² ', R ³ , R ³ R ⁴ , RRRR ⁶ and R ⁶ ' are each independently  (i) a hydrogen atom; (Ii) -NR ²⁰ R ²¹ (wherein, R ² ° and R ²¹ are each independently a hydrogen atom, or at any good CC alkyl group optionally substituted by a halogen atom);  (i i i) Siano group;  (iV) a nitro group;  (V) force rubamoyl group; (vi) N- (C ₁ -C ₄ alkyl) strong rubamoyl group; (V ii) N, N-di (C ₁ -C ₄ alkyl) strong rubamoyl group; (V iii) -NHCOR ⁹ (wherein R ⁹ is a branched and optionally substituted alkyl group of 0 ^ to 0 ₄ );  (ix) an alkyl group of Ci Ce which may form a branch or a ring and may be substituted with a halogen atom; (X) may be branched or ringed and substituted with a halogen atom Can have, an alkenyl group of C ₂ -C _e; (xi) may form a branched or cyclic and may be substituted with a halogen atom, an alkynyl group of C ₂ -C _6;  (x i i) aralkyl group, wherein the aryl moiety constituting the aralkyl group is  An alkyl group which may be branched and may be substituted with a halogen atom; A C ₁ -C ₅ anoloxy group which may be branched and optionally substituted with a haguchigen atom, A halogen atom, a C ₁ -C ₄ alkyl group, a cyano group, or _NR ² , which may be branched and substituted with a halogen atom; R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a Ci to C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a force Rubamoiru group, N-(~ alkyl) force Rubamoiru group, N, N-di (C ₁ -C ₄ alkyl Le) force Rubamoiru group or a NHCOR ⁹ (here, may and halogen be R ⁹ is branched, A C ₁ -C ₄ alkyl group optionally substituted with an atom), an aryl group,  Ciano group, -NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a C i to C ₄ alkyl group optionally substituted with a halogen atom),  Nitoguchi,  Force rubymoyl group, N— (C ₁ -C ₄ alkyl) N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group, -NHCOR ⁹ (where R ⁹ may be branched and is a halogen atom) An optionally substituted Ci C alkyl group), and  Halogen atom An aralkyl group optionally substituted with at least one group selected from the group consisting of:  (X i i i) A heteroaralkyl group having a heteroaryl moiety, wherein the heteroaryl moiety is  An alkyl group which may be branched and optionally substituted with a halogen atom, A C to C ₅ alkoxy group which may be branched and optionally substituted with a halogen atom, Halogen atom, which may be branched and optionally substituted with a halogen atom CC alkyl group, cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently hydrogen A C ₁ -C ₄ alkyl group optionally substituted by an atom or a halogen atom), a nitro group, a strong rubamoyl group, N- (C ₁ -C ₄ alkyl) a strong rubamoyl group, N, N— di (~ Ji alkyl Le) force Rubamoiru group or a NHCOR ⁹ (wherein, R ⁹ is Ji may be substituted with well and halogen atoms be branched-^ alkyl group), substituted by Maybe, Aryl group,  Ciano group, -NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a C! -C ₄ alkyl group optionally substituted with a halo atom),  Nitro group,  Force rubymoyl group, N— (C ₁ -C ₄ alkyl) force rubamoyl group, N, N—di (dialkyl), rubamoyl group, -NHCOR ⁹ (wherein R ⁹ may be branched and may be substituted with a halogen atom! ~ Ji is an alkyl group), and  Halogen atom A heteroaralkyl group optionally substituted with at least one group selected from the group consisting of:  (X i v) aryl group, where the aryl group is Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group, Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group, Halogen atoms, branched C ₁ -C ₄ optionally substituted at good and halogen atoms have an alkyl group, Shiano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently A hydrogen atom or an alkyl group which may be substituted with a halogen atom), a two-necked group, a strong rubamoyl group, N— (C ₁ -C ₄ alkyl) a strong rubamoyl group, N, N —Di (di-alkyl), a strong rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and substituted with a C 1 -C ₄ alkyl group, An aryl group, which may be substituted with  Ciano group, _ _NR 20 _R 21 (where 'R 2 and R ₂₁ may each independently be replaced with a hydrogen atom or a halogen atom)

An alkyl group)  Nitro group,  Canolevamoyl group,  N- (ji-ji alkyl) rubamoyl group, N, N-di (Ci C alkyl) force rubermoyl group, NHCOR ⁹ (wherein R ⁹ may be branched and substituted with a halogen atom)

An alkyl group),  A halogen atom, and S (O) _n -R (where n is 0, 1 or 2 and R is a Ci C alkyl group which may be branched and substituted with a halogen atom) May be substituted with at least one group selected from the group consisting of or O- (CH ₂ ) _m -0- (where m is 1 or 2 Which may be substituted with an aryl group;  (X V) heteroaryl group, wherein the heteroaryl group is Branched even if well and Ha port Gen atoms optionally substituted C ~ C ₄ alkyl group,  A C Cs alkoxy group which may be branched and optionally substituted with a haguchi atom, A halogen atom, which may be branched and may be substituted with a halogen atom, an alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently A hydrogen atom or an alkyl group which may be substituted with a halogen atom), a nitro group, a strong rubamoyl group, an N- (di-alkyl), an N-N-di (di- Alkyl) may be substituted with a strong rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and may be substituted with a halogen atom, which is an alkyl group). , Aryl group,  Ciano group, _ _NR 20 _R 21 (where 1 ^2. Oyobi 1 21 are each independently either hydrogen atom, or at any good C ₁ -C ₄ alkyl group optionally substituted by a halogen atom), Nitro group,  Force rubymoyl group,  N- (ji ^ ~ ji alkyl) force ruberamoyl group,  N, N-di (Ci C alkyl) force rubermoyl group, -NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and  Halogen atom A heteroaryl group optionally substituted with at least one group selected from the group consisting of:  (X V i) halogen atom;  A group selected from the group consisting of: R ⁷ may form a branch or a ring and may be substituted with a halogen atom C _{13 to} C ₃ . An alkyl group of R ^8, which may be branched or form a ring and may be substituted with a halogen atom, an alkyl group of C ₁ -C _30, and X- is a halide Anion, S CN_, HS_〇 ₄ one, and HF ₂ - is Anion selected from the group Ru Tona. 2. I ¹ , R ¹ ', R ² , R ² ', 'R ³ , R ³ ', R ⁴ , R ⁴ ', R ⁵ , R ⁵ ', R of the compound represented by the formula (I) ⁶ and R ⁶ 'force each independently,  (i) a hydrogen atom;  (X i V) aryl group, where the aryl group is  Ci ^ C alkyl group which may be branched and may be substituted with a halogen atom, A C ₁ -C ₅ anoalkoxy group which may be branched and optionally substituted with a halogen atom, C atoms, which may be branched and may be substituted with a halogen atom Ci C alkyl group, cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently A hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl group, N— (di-^^ alkyl) a strong rubamoyl group, N, N-di (. ^ ~ Ji alkynole) Forced rubermoyl group, or one NHCOR ⁹ (where R ⁹ may be branched and substituted with a Haguchizan atom C i ~ C _An alkyl group), an aryl group,  Ciano group, _ _NR 2 O _r21 (where, 1 ^ ² ° Oyopi 1 ²¹ are each independently a hydrogen atom, or at or C port Gen atoms optionally substituted C. ~ C ₄ alkyl group is there) ,  Nitro group,  Force rubymoyl group, N- (C ₁ ~C ₄ alkyl) force Rubamoiru group,  N, N-di (Ci C alkyl) force rubermoyl group, -NHCOR ⁹ (wherein R ⁹ may be branched and may be substituted with a halogen atom. ~ ^ Is an alkyl group),  Halogen atoms and — S (O) _n -R (where n is 0, 1 or 2 and R may be branched and optionally substituted with a C atom C ₄ C ₄ alkyl Group); Or may be substituted with at least one group selected from the group consisting of 0_ (CH ₂ ) _m -0- (where m is 1 or 2 is there) Optionally substituted by an aryl group; and (XV) heteroaryl group, wherein the heteroaryl group is Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group,  C! Cs alkoxy group which may be branched and optionally substituted with a halogen atom, A halogen atom, which may be branched and optionally substituted with a halogen atom, a Ci C alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently A hydrogen atom, or a Ci C alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl 'group, an N- (C ₄ -C ₄ alkyl) strong rubamoyl group, N, N-di ( Ji ~. ^^ alkyl ') with a strong rubermoyl group, or with one NHCOR ⁹ (where R ⁹ may be branched and substituted with a halogen atom). Optionally substituted, aryl group,  Ciano group, _{_NR} 20 _R 21 (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogene atom),  Nitro group,  Carpamoyl group, N- (C ₁ ~C ₄ alkyl) force Rubamoiru group, N, N—di (C ₁ -C ₄ alkyl) carbamoyl group, -NHCOR ⁹ (where, R ⁹ is branched c ₁ may be substituted in good and halogen atom have to c ₄ alkyl group), and  Halogen atom A heteroaryl group optionally substituted with at least one group selected from the group consisting of: The compound according to claim 1, which is a group selected from the group consisting of: 3. RR ¹ ', R ² , R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ', R ⁵ , R ⁵ ', R ⁶ and R ^{6 of the} compound represented by the formula (I) 'Force each independently, hydrogen atom, 3, 4, 5—trifluorophenyl group, 3, 4, 5 _trichlorophenyl phenyl group, 3,4-difluorophenyl group, 3 _nitrophenyl group, 3-cyanophenyl group, benzo, thiophenyl-2-yl group, 3,5-difluorophenyl group, 3-trifluoromethylenophenyl group, 2,4-difluorophenyl group, 3-methylsulfurylphenyl group, 3,5-bis (trifnoleolomethinole) phenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 4-trifluoromethyl phenyl group, and 3,5-bis (3,5,1bis (trifnoreolomethyl) A group selected from the group consisting of a phenyl group, 2. The compound according to 2. 4. The compound represented by the above formula (I) is represented by the following formula (1 ′)

) (Where R ¹ and R ¹ ′ are each independently a hydrogen atom, 3, 4, 5-trifluorophenyl group, 3, 4, 5-trichlorophenyl group, 3, 4-difluorophenylenole Group, 3-bistrophenyl group, 3-cyanobenyl group, benzothiophenyl-2-yl group, 3,5-difluorophenyl group, 3-trifluoromethylphenyl group, 2,4-difluorophenyl 3-methylsulfurphenyl group. 3,5-bis (trifluoromethyl) phenyl group, 4- Selected from the group consisting of a nitrophenyl group, a 4_cyanophenyl group, a 4-trifnoleolomethinophenyl group, and a 3,5-bis (3 ', 5'-bis (trifluoromethyl) phenyl) phenyl group And R ⁷ , R ^8, and X_ are each independently a compound defined as in claim 1), Compound. 5. The compound according to claim 1, wherein R ^{7 of the} compound represented by the formula (I) is a C _{13 to} C ₂₂ alkyl group which may form a branch or a ring. 6. The compound according to claim 5, wherein R ⁷ and R ⁸ of the compound represented by the formula (I) are the same. 7. A process for producing a compound represented by formula (I) according to claim 1, comprising: The following formula (I I):

In the presence of an acid scavenger in an organic solvent, the compound represented by The following formula (III)

A step of reacting with a secondary amine represented by: Where in equation (II) ^{R \ R, R 2, R} 2 ', R 3, R 3', R 4, R 4 ', R 5, R 5', R 6 and R ⁶ 'are each independently,  (i) a hydrogen atom; (ii) -NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a C! to C ₄ alkyl group optionally substituted with a haguchi atom) ) ';  (i i i) Siano group;  (i v) Futabaguchi group;  (V) force rubamoyl group; (vi) N— (C ₁ -C ₄ alkyl) force rubamoyl group;  (V i i) N, N-di (dialkyl) rubamoyl group; (V iii) — NHCOR ⁹ (wherein R ⁹ is an alkyl 'group which may be branched and optionally substituted with a halogen'atom); (Ix) to form a branched or ring may be ¾ conversion in good and halogen atom, an alkyl group of C ₁ -C _6; (X) may form a branched or cyclic and may be substituted with a halogen atom, an alkenyl group of C ₂ -C _6; (xi) may form a branched or cyclic and may be substituted with a halogen atom, an alkynyl group of C ₂ -C _6;  (X i i) aralkyl group, wherein the aryl moiety constituting the aralkyl group is Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group, Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group, A halogen atom, which may be branched and optionally substituted with a halogen atom, a C to C ₄ alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently A hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl group, N- (Ci C alkyl) a strong rubamoyl group, N, N— Di (Ci C alkyl ') force rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and substituted with a halogen atom). Optionally substituted, aryl group,  Ciano group, -NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a C ₄ to C ₄ alkyl group optionally substituted with a haguchi atom),  Nitro group,  Force rubymoyl group,  N— (ji-ji alkyl) strong rubermoyl group, N, N-di (C ₁ -C ₄ alkyl;) force rubamoyl group, -NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and optionally substituted with a halogen atom), and  Halogen atom An aralkyl group optionally substituted with at least one group selected from the group consisting of:  (x i i i) a heteroaralkyl group having a heteroaryl moiety, wherein the heteroreel moiety is  An alkyl group which may be branched and optionally substituted with a halogen atom, _May be branched and may be substituted with a halogen atom CC ₅ Ar'oxy group, Halogen atom, which may be branched and optionally substituted with a halogen atom Ci to C ₄ alkyl group, cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently Or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a force << / levamoyl group, an N-alkyl) force rubermoyl group, N, N —Di (.- alkyl) Forced rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ is a C ₁ -C ₄ alkyl group which may be branched and substituted with a halogen atom) Optionally substituted with an aryl group,  Ciano group, _{_NR} 20 _R 21 (where R ² ° and R ²¹ are each independently a hydrogen atom or an alkyl group optionally substituted with a halogen atom),  Nitro group,  Carpamoyl group, N- (C ₁ ~C ₄ alkyl) force Rubamoiru group, N, N—di (C ₁ -C ₄ alkyl) carbamoinole group, -NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and  Halogen atom A heteroaralkyl group optionally substituted with at least one group selected from the group consisting of:  (x i v) aryleno group, wherein the aryl group is  An alkyl group which may be branched and optionally substituted with a halogen atom, C _{1 to} C ₅ may be branched and may be substituted with a halogen atom An alkoxy group,  A halogen atom, which may be branched and substituted with a halogen atom 'May be an alkyl group, a cyano group, one NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a permanent atom or an optionally substituted halogen atom) ₄ is or an alkyl group), a nitro group, a force Rubamoiru group, Ν- (C ₁ ~C ₄ alkyl ') force Rubamoiru group, N, N-di (Ji-Ji alkyl Le) Karupamoiru group or a NHCOR ^9, ( Here, R ⁹ is a Ci C alkyl group which may be branched and may be substituted with a halogen atom). An aryl group which may be substituted with  Ciano group, _{_NR} 20 _R 2 i (where R ² ° and R ²¹ are each independently a hydrogen atom or a ₄ alkyl group optionally substituted with a haguchi atom),  Nitro group,.  Force rubymoyl group, N— (C ₁ -C ₄ alkyl) carbamoyl group,  N, N—di (dialkyl), rubamoyl group, -NHCOR ⁹ (wherein R ⁹ is a C ₁ -C ₄ alkyl group which may be branched and may be substituted with a halogen atom),  A halogen atom, and — S (O) _n -R (where n is 0, 1 or 2 and R is an alkyl group which may be branched and substituted with a halogen atom) May be substituted with at least one group selected from the group consisting of: or _〇1 (CH ₂ ) _m ~ 0- (where m is 1 or 2) optionally substituted with an aryl group; (XV) a heteroaryl group, wherein the heteroaryl group is  Ci C alkyl group which may be branched and may be substituted with a haguchi atom, Branched c ₁ may be substituted in good and halogen atom have to c ₅ alkoxy group, Halogen atom, which may be branched and optionally substituted with a halogen atom CC alkyl group, cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently hydrogen N- (C ₁ -C ₄ alkyl) force rubermoyl group, N, N-di (C) which is an atom or a CC ^ alkyl group optionally substituted with a halogen atom) _{1 to} C ₄ alkyl) substituted with a strong rubermoyl group, or one NHCQR ⁹ (wherein R ⁹ may be branched and substituted with a halogen atom) May have been, allyl group,  Ciano group, -NR ²⁰ R ²¹ (wherein R ² ° and R ²¹ are each independently a hydrogen atom or an alkyl group optionally substituted with a halogen atom),  Nitro group,  Power ruber moyl group,. N— (C ₁ -C ₄ alkyl) force rubamoyl group, N, N—di (C ₁ -C ₄ alkyl) carbamoyl group, -NHCOR ⁹ (wherein R, ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and  Halogen atom A heteroaryl group optionally substituted with at least one group selected from the group consisting of: (xvi) 'mouth' gen atom;  A group selected from the group consisting of and Z is a halogen atom, And in the formula (I I I) R ⁷ is a C ₁₃ -C ₃₀ alkyl group which may form a branch or a ring and may be substituted with a halogen atom; and R ⁸ is a C _{1 to} C ₃₀ alkyl group, which may form a branch or a ring and may be substituted with a halogen atom. 8, the formula R ¹ R ¹ of the compound represented by ^{(II) ', R 2,} R 2', R 3, R 3 ', R 4, R 4' -, R 5, R 5 ', R 6 And R ⁶ 'force each independently,  (i) a hydrogen atom;  (X i V) aryl group, where the aryl group is It may be branched and substituted with a halogen atom

An alkyl group, Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group, A halogen atom, which may be branched and may be substituted with a halogen atom; an alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently , A hydrogen atom, or an alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl group, N— (C ₁ -C ₄ alkyl) a strong rubamoyl group, N, N—di (C _{1 to} C ₄ alkyl) substituted with a strong rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ is a C i to C ₄ alkyl group which may be branched and optionally substituted with a halogen atom) May have been, allyl group, Ciano group, _{_NR} 20 _{R 2 1} (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C ₄ to C ₄ alkyl group optionally substituted with a halogen atom),  Nitro group,  Force rubymoyl group, N- (C ₁ -C ₄ alkyl ') force rubamoyl group, N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group, -NHCOR ⁹ (wherein R ⁹ is a c ₁ -c ₄ aralkyl group which may be branched and may be substituted with a halogen atom),  Halogen atoms and — S-(O) _n -R (where n is 0, 1 or 2 and R is a branched or substituted CC alkyl group which may be substituted with a halogen atom) ; May be substituted with at least one group selected from the group consisting of: O— (CH ₂ ) _m — O— (where m is 1 or 2 Is) Optionally substituted by an aryl group; and  (XV) a heteroaryl group, wherein the heteroaryl group is Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group, Branched even if good and ₅ alkoxy group which may be substituted with a halogen atom, A halogen atom, which may be branched and may be substituted with a halogen atom, an alkyl 'group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently A hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a rubamoyl group, N— (C ₁ -C ₄ alkyl) force rubamoyl group, N, N—di (C ₁ -C ₄ alkyl) force rubamoyl group, or one NHCOR ⁹ (where R ⁹ may be branched and A Ci C alkyl group optionally substituted with a halogen atom), an aryl group,  Ciano group, _{_NR} 20 _R 21 (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogene atom),  Nitro group,  Power Lubamoi.  N —- (di-alkyl) force rubermoyl group, N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group, -NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and optionally substituted with a halogen atom), and  Neurogen atom A heteroaryl group optionally substituted with at least one group selected from the group consisting of:  The method according to claim 7, wherein the group is selected from the group consisting of: 9. I ¹ , R ¹ ′, R ² , R ² ′, R ³ , R ³ ′, R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′, R ^{6 of the} compound represented by the formula (II) And R ⁶ 'force S, independently of each other, a hydrogen atom, 3, 4, 5—trifnoleolophenylenole group, 3, 4, 5—trichlorophenyl group, 3, 4-difluorophenyl group, 3-nitrophenyl group Group, 3-cyanophenyl group, benzothiophenyl-1-yl group, 3,5-difluorophenyl group, 3-trifluoromethylphenyl group, 2,4-difluorophenyl group, 3- Methylsulfonylphenyl group, 3,5-bis (trifluoromethyl) phenyl A group selected from the group consisting of: a group, 4-12 tropenyl group, 4-cyanophenenyl group, 4-trifluoromethyl phenyl group, and 3,5_bis (3 ′, 5,1bis (trifluoromethyl) phenyl) phenyl group The method of claim 8, wherein 10. The compound represented by the formula (I I) is represented by the following formula (I I ′):

(11,) (Wherein R ¹ and R ¹ ′ are each independently a hydrogen atom, 3, 4, -5-trif / reo-open phenyl group, 3, 4, 5-trichloro-open phenyl group, 3, 4-di Fluorophenyl group, 3-diphenyl group, 3-cyanophenyl group, benzothiophenyl 2-yl group, 3,5-difluorophenyl group, 3-trifluoromethylphenyl group, 2,4-difluorophenyl group , 3-methylsulfurphenyl group, 3,5-bis (trifluoromethyl) phenyl group, 4-nitronitro group, 4-cyanophenyl group, 4-trifluoromethylphenyl group, and 3,5-bis (3 ,, 5, bis (trifluoromethyl) phenyl) furyl group, and R ⁷ , R ⁸ and Z are each independently the same as in claim 9 Is a group defined in The method of claim 9, wherein the compound is a represented compound. . 1 1. The method according to claim 7, wherein R ^{7 of the} secondary amine represented by the formula (II) is a C _{13 to} C ₂₂ alkyl group which may form a branch or a ring. 12. The compound according to claim 11, wherein R ⁷ and R ⁸ of the secondary amine represented by the formula (II) are the same. 13. Compound represented by formula (V I):

A method for stereoselectively producing  Pure formula for axial asymmetry (I):

A compound represented by formula (IV) using a compound as a phase transfer catalyst:

A compound of formula (V) in the presence of an inorganic base in a medium Alkylating with R ¹⁸ -W (V), Where in formula (I) R \ R ¹ 'R ² , R ² ', R ³ , R ³ ,, R ⁴ , R ⁴ ', R ⁵ , R ⁵ ', R ⁶ and R ⁶ 'are each independently  (i) a hydrogen atom; (Ii) -NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently a hydrogen atom, or at any good C ₁ -C ₄ alkyl group optionally substituted by a halogen atom);  (i i i) Siano group;  (iV) nitro;  (V) force rubamoyl group; (vi) N— (C ₁ -C ₄ alkyl ′) force rubamoyl group; (V ii) N, N-di (C ₁ -C ₄ alkyl) strong ruby group; (viii) -NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and may be substituted with a halogen atom); Alkyl group of (ix) to form a branched or cyclic 'may be replaced by an atom, C ₁ -C _6' is good and halogen; (X) may form a branched or cyclic and may be substituted with a halogen atom, an alkenyl group of C ₂ -C _6; (X i) may form a branched or cyclic and may be substituted with a halogen atom, an alkynyl group of C ₂ -C _6;  (X i i) aralkyl group, wherein the aryl moiety constituting the aralkyl group is Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group, Ci to C ₅ alkoxy group which may be branched and may be substituted with a halogen atom, A halogen atom, which may be branched and substituted with a halogen atom Ci C alkyl group, Cyano group, one NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or an optionally substituted halogen atom)

N- (C ₁ -C ₄ alkyl) force rubamoyl group, N, N—di (C ₁ -C ₄ alkyl) force rubamoyl group, or one NHCOR ⁹ (wherein R ⁹ is a C i to C ₄ alkyl group which may be branched and may be substituted with a halogen atom), an aryl group,  Ciano group, -NR ²⁰ R ²¹ (wherein R ^{2 <3} and R ²¹ are each independently a hydrogen atom or a CC alkyl group optionally substituted with a halo atom)  Nitro group,  Force ruby moile 'group, N- (C ₁ -C ₄ alkyl) force rubermoyl group,  N, N-di (di-alkyl) carbamoyl group, -NHCOR ⁹ (where, R ⁹ is branched c ₁ may be substituted in good and halogen atom have to c ₄ alkyl group), and  Halogen atom An aralkyl group optionally substituted with at least one group selected from the group consisting of:  (x i i i) a heteroaralkyl group having a heteroaryl moiety, wherein the heteroaryl moiety is  Ci C alkyl group which may be branched and may be substituted with a halogen atom, A C Cs alkoxy group which may be branched and may be substituted with a halogen atom, Halogen atoms, branched and have well and which may be CC alkyl group substituted with a halogen atom, Shiano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ Oyo Pi 1 ²¹ are each independently hydrogen A C ₁ -C ₄ alkyl group which may be substituted by an atom or a halogen atom), a nitro group, a strong rubamoyl group, an N- (di-alkyl) and a N, N-di (Ci C alkyl) substituted with a rubamoyl group, or one NHCOR ⁹ (wherein R ⁹ is a C ₁ -C ₄ alkyl group which may be branched and optionally substituted with a halogen atom). You may have an ariel group,  Ciano group, _{_NR} 20 _R 21 (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C i to C ₄ alkyl group optionally substituted with a haguchi atom),  Nitro group,  Force rubymoyl group,  N- (ji-ji alkyl) rubamoyl group, N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group, -NHCOR ⁹ (where, R ⁹ is branched c ₁ may be substituted in good and halogen atom have to c ₄ alkyl group), and  Halogen atom A heteroaralkyl group optionally substituted with at least one group selected from the group consisting of:  (X i V) aryl group, where the aryl group is Branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group, Ci Cs alkoxy group which may be branched and may be substituted with a halogen atom, A halogen atom, which may be branched and substituted with a halogen atom. An alkyl group, a cyano group, one NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a Ci C alkyl group optionally substituted by a halogen 'atom) ), Nitro group, force rubamoyl group, N— (C! C alkyl) force rubamoyl group, N, N—di (C ₁ -C ₄ alkyl ′) force rubamoyl group, or one NHCOR ⁹ (where R ⁹ is a C ₁ -C ₄ alkyl group which may be branched and may be substituted with a halogen atom), an aryl group,  Ciano group, _{_NR} 20 _R 21 (where R ² ° and R ²¹ are each independently a hydrogen atom or a C i to C ₄ alkyl group optionally substituted with a haguchi atom),  Nitro group,  Force rubymoyl group, N- (C ₁ ~C ₄ alkyl) Karupamoiru groups,  N, N—di (dialkyl), rubamoyl group, -NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom),  A halogen atom, and S (O) _n -R (where n is 0, 1 or 2 and R may be branched and substituted with a halogen atom). is there) It may be substituted with at least one group selected from the group consisting of: O— (CH ₂ ) _m — O— (where m is 1 or 2) Which may be substituted with an aryl group; (XV) heteroaryl group, wherein the heteroaryl group is C-dialkyl group which may be branched and may be substituted with a halogen atom,  A C Cs alkoxy group which may be branched and may be substituted with a halogen atom, A halogen atom may be branched and may be substituted with a halogen atom. ^ ~ Ji alkyl group, cyano group, one NR ² . R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom or a halogen ′ atom which may be substituted with an alkyl group), a nitro group, a rubamoyl group , N— (. Alkyl) force rubermoyl group, N, N—di (Ci C alkyl ′) force rubermoyl group, or one NHCOR ⁹ (where R ⁹ may be branched and is a halogen atom) An optionally substituted C _{1 to} C ₄ alkyl group), an aryl group,  Ciano group, -NR ²⁰ R ²¹ (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom) ,  Nitro group,  Canolevamoyl group, N- (Ci-C ₄ alkyl) force rubermoyl group, N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group, One NHCOR ⁹ (wherein R ⁹ is a Ci to C ₄ alkyl group which may be branched and optionally substituted with a halogen atom), and  Halogen atom A heteroaryl group optionally substituted with at least one group selected from the group consisting of: (x V i) a neurogenic atom; A group selected from the group consisting of forces, R ⁷ may form a branch or a ring and may be substituted with a halogen atom C _{13 to} C ₃ . An alkyl group of R ⁸ is a Ci C ^ alkyl group, which may form a branch or a ring and may be substituted with a halogen atom, and X is a halide anion, In formula (I V) and formula (V I), R ¹⁴ and R ¹⁵ are each independently  (i) a hydrogen atom; or  (i i) an aryl group, the aryl group  An alkyl group which may be branched and optionally substituted with a halogen atom,  Ci Cs alkoxy group which may be branched and may be substituted with a halogen atom, Halogen atom, which may be branched and optionally substituted with a halogen atom CC alkyl group, cyano group, one NR ³⁰ R ³¹ (where R ³⁰ and R ³¹ are each independently hydrogen Or a Ci C alkyl group optionally substituted by a halogen atom), a nitro group, a strong rubamoyl group, an N— (dialkyl), an N, N-di (Ci C alkyl) No) A rubamoyl group, or one NHCOR ⁹ (wherein R ⁹ is a c _{1 to} c ₄ alkyl group which may be branched and may be substituted with a halogen atom). , Aryl group,  Ciano group, '. _{_NR} 30 _R 31 (wherein R 3 and R 31 are each independently a hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), Nitro group,  Canolevamoyl group, N- (C ₁ ~C ₄ alkyl) Karupamoiru group,  N, N—di (C C alkyl ') force rubermoyl group, -NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and  Halogen atom An aryl group optionally substituted with at least one group selected from the group consisting of: Except that R ¹⁴ and R ¹⁵ are both hydrogen atoms, R ¹⁶ is- (i) a hydrogen atom; (ii) C _{1 to} C ₁ which may form a branch or a ring and may be substituted with a halogen atom. Wherein the alkyl group is ₅ to ₅ alkoxy groups which may be branched and may be substituted with a halogen atom,  Ciano group, _{_NR} 30 _R 31 (wherein R ³ ° and R 31 are each independently a hydrogen atom or a C ₄ to C ₄ alkyl group optionally substituted with a halo atom), '  Nitro group,.  Force 7 Repamoinole group,  N— (Ci C alkyl) force rubermoyl group,  N, N-di (Ci C alkyl) force rubermoyl group, -NHCOR ⁹ (wherein R ⁹ is a CC alkyl group which may be branched and may be substituted with a halogen atom), Halogen atoms, -COR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and -CO ₂ R ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and optionally substituted with a halogen atom) An alkyl group optionally substituted with at least one group selected from the group consisting of: (Iii) may form a branched or cyclic and may be substituted with a halogen atom, an alkenyl group of c ₂ to c _6; (I V) to form a branched or ring may be substituted in good and halogen atom, an alkynyl group of c ₂ to c _6; (V) Ararukiru a group, the Ararukiru group and may be Ariru portion constituting the branched and optionally substituted with C port Gen atoms C i to C ₄ alkyl group, A C to C ₅ alkoxy group which may be branched and optionally substituted with a halogen atom, A halogen atom, which may be branched and optionally substituted with a halogen atom, an alkyl group, a cyano group, one NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are each independently a hydrogen atom; Or a Ci C alkyl group optionally substituted with a halogen atom), a nitro group, a strong rubamoyl group, N— ₄ alkyl) a strong rubamoyl group, N, N—di (C ₁ -C ₄ alkyl) ) A rubamoyl group, or an NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and optionally substituted with a halogen atom), an aryl group,  Ciano group, In _ _NR 20 _R 21 (wherein, R20 and R2i are each independently hydrogen An CC or an alkyl group optionally substituted with a halogen atom),  Nitro group,  Force rubymoyl group, N— (C ₁ -C ₄ alkyl) force rubamoyl group,  N, N-di (Ci C alkyl) force rubermoyl group, -NHCOR ⁹ (wherein R ⁹ is a Ci to C ₄ alkyl group which may be branched and optionally substituted with a halogen atom), and  Halogen atom May be substituted with at least one group selected from the group consisting of, and the alkyl moiety constituting the aralkyl group may form a branch or a ring and be substituted with a halogen atom. also Ru good C ₁ -C ₆ alkyl 'Motodea, Ararukiru group;  (v i) a heteroaralkyl group having a heteroaryl moiety, wherein the heteroaryl moiety is  A C C alkyl group which may be branched and optionally substituted with a halogen atom, Branched C ₁ may be substituted in good and halogen atoms have -C ₅ alkoxy group, A halo atom, which may be branched and substituted with a halo atom; an alkyl group, a cyano group, _NR ²⁰ R ²¹ (where R ²⁰ and R. ²¹ are Each independently a hydrogen atom or an alkyl group which may be substituted with a halogen atom), a nitro group, a strong rubamoyl group, N— (C ₁ -C ₄ alkyl carbamoyl group, N , N-di (C ₁ -C ₄ alkyl) force rubamoyl group, or one NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom) ) Optionally substituted with an aryl group,  Ciano group, _ _NR 20 _R 21 (wherein R 2 and are each independently a hydrogen atom or an alkyl group optionally substituted with a halogen atom),  Nitro group,  Force rubymoyl group,  N- (^^ ~. Alkyl) Force rubermoyl group N, N—di (C ₁ -C ₄ alkyl) force rubamoyl group, -NHCOR ⁹ (wherein R ⁹ is a Ci to C ₄ alkyl group which may be branched and optionally substituted with a halogen atom), and  Halogen atom A heteroaralkyl group optionally substituted with at least one group selected from the group consisting of:  (v i i) aryl group, A c ₁ -c ₄ alkyl group which may be branched and optionally substituted with a halogen atom,  Ci Cs alkoxy group which may be branched and may be substituted with a halogen atom, A halogen atom, which may be branched and may be substituted with a halogen atom, a CC alkyl group, a cyano group, one NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ are independently hydrogen A C ₁ -C ₄ alkyl group which may be substituted with an atom or a halogen atom), a nitro group, a strong rubamoyl group, N— (Ci C alkyl) a strong rubamoyl group, N, N-dialkyl ) Power rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and may be substituted with a halogen atom) Optionally substituted with an aryl group,  Ciano group, _{_NR} 20 _R 21 (wherein R 20 and each independently represent a hydrogen atom or a Ci C alkyl group optionally substituted with a haguchi atom),  Nitro group,  Force rubymoyl group, N- (C ₁ -C ₄ alkyl) force rubermoyl group,  N, N—di (Ci C alkyl ') carbamoyl group, -NHCOR ⁹ (wherein R ⁹ is a Ci to C ₄ alkyl group which may be branched and optionally substituted with a halogen atom), and  Neurogen atom An aryl group optionally substituted with at least one group selected from the group consisting of:  '(V i i i) heteroaryl group, Branched even if well and optionally substituted C E also be ~ C ₄ alkyl group with a halogen atom, Branched c ₁ may be substituted in good and halogen atom have to c ₅ alkoxy group, A halogen atom, which may be branched and optionally substituted with a halogen atom, a Ci C alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently or hydrogen atom, or at or even better C ₁ -C ₄ alkyl group optionally substituted by a halogen atom), a nitro group, a force Rubamoiru group, N- (C ₁ ~C ₄ alkyl) force Rubamoiru group, N, N —Di (C ₁ -C ₄ alkyl) Forced rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and substituted with a halogen atom C ₁ -C ₄ alkyl) Group) Optionally substituted with an aryl group,  Ciano group, _{_NR} 20 _{R 2 1} (wherein R 20 and each independently represent a hydrogen atom or a C ₁ to C ₄ alkyl group optionally substituted with a halogene atom),  Nitoguchi,  Force rubymoyl group,  N-alkyl ') strong rubermoyl group,  N, N—di (dialkyl), rubamoyl group, -NHCOR ⁹ (wherein R ⁹ is an alkyl group which may be branched and may be substituted with a halogen atom), and  Halogen atom A heteroaryl group optionally substituted with at least one group selected from the group consisting of:  A group selected from the group consisting of: R ¹⁷ is an ₈ alkyl group which may form a branch or a ring and may be substituted with a halogene atom; In formula (V) and formula (V I), R ¹⁸ is (i) C _{1 to} C ₁ which may form a branch or a ring and may be substituted with a halogen atom. Wherein the alkyl group is Branched optionally substituted in well and halogen atoms have C i to C ₅ Anorekokishi group,  Ciano group, _ _NR 30 _R 3! (Where R3 and R ³¹ are each independently a hydrogen atom or a C ₁ -C alkyl group optionally substituted with a halogen atom) )  Nidro group,  Force rubymoyl group,  N— (ji-ji alkyl) rubamoyl group, N, N-di (C ₁ -C ₄ alkyl ') force rubamoyl group, -NHCOR ⁹ (wherein R ⁹ is a Ci C alkyl group which may be branched and may be substituted with a halogen atom),  Halogen atom -COR ⁹ (wherein R ⁹ is a branched or optionally substituted alkyl group with a halogen atom), and — C0 ₂ R ⁹ (wherein R ⁹ is a C _{1 to} C ₄ alkyl group which may be branched and substituted with a halogen atom) ■ at least one selected from the group consisting of An aralkyl group optionally substituted by a group; (Ii) may form a branched or cyclic and may be substituted with a halogen atom, Ariru or substituted Ariru group C ₃ -C _9; And (iii) to form a branched or ring may be substituted in good and halogen 'atom, an alkenyl group of C ₂ -C _6; (Iv) may form a branched or cyclic and may be substituted with a halogen atom, an alkynyl group of C ₂ -C _6; (V) Ararukiru an group, the Ararukiru group constituting Ariru parts branched C ₁ may be substituted in good and halogen atoms optionally -C ₄ alkyl group,  A C Cs alkoxy group which may be branched and may be substituted with a halogen atom, A halogen atom, which may be branched and substituted with a halogen atom Or a C i C alkyl group, a cyan group, or one NR ²⁰ R ²¹ (wherein R ²⁰ and R ²¹ may each independently be a hydrogen atom or a halogen atom). N- (Ci C alkyl-bearing rubermoyl group, N, N-di (Ci ^^ C alkyl) -bearing rubermoyl group, or one NHCOR ⁹ R ⁹ may be branched and is a Ci to C ₄ alkyl group which may be substituted with a halogen atom), an aryl group,  Ciano group, _{_NR} 20 _R 21 (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C to C ₄ alkyl group optionally substituted with a halo atom),- Nitro group,  Force rubymoyl group, N— (C ₁ -C ₄ alkyl) force rubamoyl group, N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group, -NHCOR ⁹ (where, R ⁹ is branched c ₁ may be substituted in good and halogen atom have to c ₄ alkyl group), and  Halogen atom May be substituted with at least one group selected from the group consisting of, and the alkyl moiety constituting the aralkyl group may form a branch or a ring and be substituted with a halogen atom. An aralkyl group which is a c ₁ -c ₆ alkyl group;  (v i) Heteroalkyl S having a heteroreel portion, wherein the heteroreel portion is An alkyl group which may be branched and optionally substituted with a halogen atom, Branched c ₁ may be substituted in good and halogen atom have to c ₅ alkoxy group, Halogen atoms, branched C ₁ -C ₄ optionally substituted at good and halogen atoms have an alkyl group, Shiano group, one NR ²⁰ R ²¹ (wherein, R ²⁰ and R ²¹ are each independently A hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted with a halogen atom), a nitro group, a cal'pamoyl group, an N- (dialkyl), a rubamoyl group, N, N-di (di-alkyl) carbamoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and may be substituted with a halo atom, Ci to C ₄ alkyl group) Which may be substituted with an aryl group,  Ciano group, -NR ^{20 21} (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C ₄ to C ₄ alkyl group optionally substituted by a haguchi atom),  Nitro group,  Carpamoyl group, N— (C ₁ -C ₄ alkyl) force rubamoyl group,  N, N-di (. Alkyl) force rubermoyl group, NHCOR ⁹ (wherein R ⁹ is a C ₁ -C ₄ alkyl group which may be branched and optionally substituted with a halogen atom), and  Neurogen atom A heteroaralkyl group optionally substituted with at least one group selected from the group consisting of: (V ii) may be branched and may be substituted with a halogen atom, a C ₃ to C ₉ propargyl group or a substituted argyl group; A group selected from the group consisting of In equation (V) W is a functional group having a leaving ability, And in the formula (V I)  * Indicates a newly generated asymmetric center. 14. RR ¹ ′, R ² , R ² ′, R ³ , R ³ ′, R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′, R ⁶ and R ^{6 of the} compound represented by the formula (I) 'Force each independently,  (i) a hydrogen atom;  (X i V) aryl group, where the aryl group is  〇 to 〇 Ar'alkyl group which may be branched and may be substituted with a halogen atom; May be branched and may be substituted by a halogen atom C -C ₅ alkoxy group, A halogen atom, which may be branched and may be substituted with a halogen atom; an alkyl group, a cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently A hydrogen atom or a halogen atom, which may be substituted with an alkyl group), a nitro group, a rubamoyl group, N- (C ₁ -C ₄ alkyl) force rubamoyl group, N, N—di (Ci C alkyl) force rubamoyl group, or one NHCOR ⁹ (where R ⁹ may be branched and is a halogen atom) An optionally substituted C _{1 to} C ₄ alkyl group), an aryl group,  Ciano group, _{_NR} 20 _R 21 (wherein _R 2 and R 21 are each independently a hydrogen atom or a Ci C alkyl group optionally substituted with a haguchi atom), Nitro group, Force rubymoyl group,  N— (^^ "^ C alkyl) strong rubermoyl group, N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group, -NHCOR ⁹ (wherein R ⁹ is a c ₁ -c ₄ alkyl group which may be branched and may be substituted with a halogen atom),  Halogen atoms and — S (O) _n -R (where n is 0, 1 or 2 and R is branched and optionally substituted with a halogen atom) C ₁ -C ₄ alkyl group ); May be substituted with at least one group selected from the group consisting of: or 0 and (CH ₂ ) _ra -0- (where m is 1 or 2 Is) Optionally substituted by an aryl group; and  (XV) heteroaryl group, wherein the heteroaryl group is Branched C ₁ may be substituted with at best 'and Ha port Gen atoms optionally -C ₄ alkyl group,  ^ Ci Cg anoloxy group which may be branched and optionally substituted with a halogen atom, Halogen atom, which may be branched and may be substituted with a halogen atom 〇 to 〇 Alkyl group, cyano group, one NR ²⁰ R ²¹ (where R ²⁰ and R ²¹ are each independently , A hydrogen atom, or an alkyl group which may be substituted with a halogen atom), a nitro group, a force rubamoyl group, N— (Ci

Alkyl) Forced rubermoyl group, N, N-di (Ci C alkyl) Forced rubermoyl group, or one NHCOR ⁹ (wherein R ⁹ may be branched and substituted with a halogen atom Ci C An alkyl group), an aryl group, Ciano group, _{_NR} 20 _R 21 (wherein R ² ° and R ²¹ are each independently a hydrogen atom or a C i to C ₄ alkyl group optionally substituted with a haguchi atom),  Etro group,  Force rubymoyl group, N- (C ₁ ~C ₄ alkyl) force Rubamoiru group, N, N-di (C ₁ -C ₄ alkyl) force Rubamoiru group, -NHCOR ⁹ (wherein R ⁹ is a CC ^ alkyl group which may be branched and optionally substituted with a halogen atom), and  Neurogen atom A heteroaryl group optionally substituted with at least one group selected from the group consisting of: The method according to claim 13, which is a group selected from the group consisting of: 1 5. I ¹ , R, R ² , R ² ′, R ³ , R ³ ′, R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′, R ⁶ and the compound represented by the formula (I) R ⁶ 'force Independently of each other, hydrogen atom, 3, 4, 5-trifluorophenyl group, 3, 4, 5-trichlorophenyl group, 3, 4-difunoleorhophenol group, 3-nitrophenyl group Group, 3-cyanophenyl group, benzothiophenyl-2-yl group, 3,5-diphenolofolyl group, 3-trifluoromethylphenyl group, 2,4-difluorophenyl group, 3-methylsulfo group -Luenyl, 3,5-bis (trifnoleolomethinole) phenyl group, 4-12 tropenyl group, 4-1-cyanophenyl group, 4-1-trifluoromethylphenyl group, and 3,5-bis (3 ', 5' A bis (trifnoleolomethyl) phenyl) group selected from the group consisting of phenyl groups, The method according to claim 14. 16. The compound represented by the formula (I) is represented by the following formula (1 ′):

(Where R ¹ and R ¹ ′ are each independently a hydrogen atom, 3, 4, 5-trifluorophenyl group, 3, 4, 5-trichlorophyl 'group, 3, 4-difluorophenyl Group, 3-diphenyl group, 3-cyanophenyl group, benzothiophenyl_2-yl group, 3,5-difluorophenyl group, 3-trifluoromethyl-phenylphenyl group, 2,4-difluorophenyl group, 3-methylsulfuryl group Honinorefinole group, 3,5-bis (trifnoleolomethyl) phenyl group, 4-Nitrofeninole group, 4-cyanophenyl group, 4-trifnoleolomethyl group, and 3,5-bis (3, 5, 5, bis (trifluoromethyl) phenyl) is a group selected from the group consisting of phenyl groups, and R ⁷ , R ⁸ and X— are each independently Defined as in item 1 The method according to claim 15, which is a compound represented by: 17. The method according to claim 13, wherein R ^{7 of the} compound represented by the formula (I) is an alkyl group of 0 _{13 to} ○ ₂₂ which may form a branch or a ring. 18. The method according to claim 17, wherein R ⁷ and R ⁸ of the compound represented by the formula (I) are the same. . 19. The compound represented by the formula (I) is 0.001 mol per 1 mol of the compound represented by the formula (IV). / Used at a rate of ₀ to 5 mol%, The method according to 13. 20. The compound represented by the formula (I) is used in an amount of 0.005 mol% to 0.5 mol% with respect to 1 mol of the compound represented by the formula (IV). 19. The method according to 19. 21. A method for producing an optically active α-amino acid comprising the steps of:  21. A compound represented by the formula (V I) obtained by the method according to claim 13:

^{(Wherein, R 14, R 15, R} 16, R 17 and R ¹⁸ are the same groups as defined above) Imino group ^{(R 14 R 15 C = N_} ) and ester groups (one COSR ^{1 7)} Hydrolyzing under acidic conditions. 22. A method for producing an optically active amino acid comprising the steps of:  21. A compound represented by the formula (V I) obtained by the method according to claim 13:

(Where R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same as defined above) hydrolyzing the imino group (R ¹⁴ R ¹⁵ C = N—) under acidic conditions And the ester group (--C0 ₂ R ¹⁷ ) of the acidic hydrolyzate Hydrolyzing under basic conditions. 23. A method for producing an optically active α-amino acid comprising:  A compound represented by the formula (V I) obtained by the method according to any one of claims 13 to 20:

(Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same as defined above) hydrolysis of the ester group (one C0 ₂ R ¹⁷ ) under basic conditions And hydrolyzing the imino group (R ¹⁴ R ¹⁵ C == N—) of the basic hydrolysis product under acidic conditions.