JP2001031682A - 1,1-2-bi-2-naphthol derivative, metal complex having the same as ligand and production of optically active nitroalcohol and michael adduct - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a metal complex useful as a catalyst for various asymmetric syntheses such as an asymmetric nitroaldol reaction, asymmetric aldol reaction, asymmetric Michael reaction, etc., by using a new optically active binaphthol derivative (BINOL derivative) as its ligand. SOLUTION: This new metal complex of the formula: [Ma(Mb)x(L12-)y] [Ma, Mb are each an metal atom; (x) is 0-3; (y) is 2, 3; L1 is a lgand] is obtained by using as the ligand L1 a new 1,1'-bi-2-naphthol derivative of the formula [R is COr1 (r1 is H or the like), Or4 (r4 is H, a 1-6C alkyl or the like); R1 to R3 are each H, cyano, nitro, a halogen, a (substituted) phenyl or the like; (n) is 1-8]. The metal complex of the above formula is obtained by mixing e.g. an organic solvent solution of a metal compound of Ma [e.g.; Al(CH3)3] with an organic solvent solution of L1 and further adding an organic solvent solution of a metal compound Mb (e.g.; CH3Li).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel optically active 1,1'-bi-2-naphthol (hereinafter referred to as "BINOL").
That. ) Derivatives, novel metal complexes with this as a ligand,
The present invention also relates to a method for producing optically active nitro alcohols and optically active malonic ester derivatives (including asymmetric acetoacetic acid derivatives or asymmetric β-diketone derivatives) using the metal complex as a catalyst for asymmetric synthesis.

[0002]

2. Description of the Related Art Metal complexes having a BINOL derivative as a ligand are known as asymmetric catalysts useful for asymmetric nitroaldol reactions, asymmetric Michael addition reactions, asymmetric ring opening reactions of epoxides and asymmetric hydrophosphonylation reactions. Have been.

For example, (1) JP-A-6-154618, JP-A-6-25
No. 6270, JP-A-6-306026, JP-A-9-253502, JP-A-9-249602, JP-A-9-256563, JP-A-11-8
No. 0070,

[0004]

Embedded image {La (M) _p [(BINOL) ^2- ] _q }

(Wherein M represents Li, Na, K, p,
q represents an integer of 1 to 3. )

[0006]

Embedded image {La (M ′) _{p ′} [(BINOL derivative) ²⁻ ] _{q ′} }

(Wherein M ′ represents an alkali metal,
p 'and q' represent an integer of 1 to 3. It has been reported that an asymmetric nitro alcohol having high optical purity can be obtained by reacting various aldehydes with a nitroalkane in the presence of the metal complex represented by the formula (1).

(2) JP-A-7-265709 and JP-A-8-291178 disclose:

[0009]

Embedded image {Ln (Na) _{p "} [(BINOL derivative) ^2- ] _q" }

(Where Ln represents a rare earth element, p ″,
q ″ represents an integer of 1 to 3.)
It is described as being useful as an asymmetric catalyst for an asymmetric Michael addition reaction. (3) JP-A-8-319258 discloses that

[0011]

Embedded image {Al (Li) _{p ′ ″} [(BINOL or BI
NOL derivative) ^2- ] q '"｝

(Wherein p ′ ″ and q ′ ″ represent integers of 1 to 3) are useful as asymmetric catalysts for asymmetric Michael addition reactions and asymmetric phosphonylation reactions. It is described that there is. (4) JP-A-9-151191 discloses that

[0013]

｛Ln (M ″) _{p ″ ″} ((BINOL or BI
NOL derivative) ^2- ] _{q ""} ｝

(Where Ln represents a rare earth element, M ″ represents an alkali metal, and p ″ ″ and q ″ ″ represent 1 to 3 respectively.
Represents an integer. In the presence of the metal complex represented by the formula (1), a phosphonate compound is synthesized by reacting an imine with a phosphonate ester and then hydrolyzed to obtain an optically active 1-aminophosphonic acid derivative useful as a pharmaceutical intermediate Are described.

(5) JP-A-10-120668 describes that a rare earth metal complex catalyst comprising a BINOL ligand and a rare earth metal alkoxide is useful for an asymmetric epoxidation reaction.

(6) Also, JP-A-9-227577 discloses that

[0017]

Embedded image {Ga (Li) _{p ″ ″ ′} [(BINOL) ²⁻ ] _{q ″ ″ ′} }

(Wherein p ″ ″ ′ and q ″ ″ ″ each represent an integer of 1 to 3), and a process for producing asymmetric hydroxysulfides using the same. Is described.

As described above, there are various reports on metal complexes having BINOL or BINOL derivatives as ligands and asymmetric reactions using the same. And the above-mentioned BINO
The L complex has high asymmetric catalytic activity.

[0020]

However, these BIs
NOL and BINOL derivatives are synthesized via a complex synthetic route and are generally expensive. In addition, many of these metal complexes are decomposed (that is, the central metal is decoordinated) under the usual post-treatment conditions after the reaction, and the product and the decomposed product of the complex ( (Ligand) by column chromatography or the like.

Therefore, if the catalyst can be more easily separated from the reaction system and such a BINOL ligand can be used repeatedly, the efficiency of the reaction operation will be improved and large-scale synthesis will be possible.

For this reason, it has been desired to immobilize the BINOL metal complex on a polymer by some method.

The present invention has been made in view of the above circumstances, and has a polymer BINOL derivative having a BINOL derivative immobilized on a polymer, a metal complex having the BINOL derivative as a ligand, and an asymmetric metal complex having the BINOL derivative as a ligand. An object of the present invention is to provide a method for producing an optically active nitro alcohol and an optically active Michael adduct used as a catalyst.

[0024]

In order to solve the above-mentioned problems,
The present inventors have synthesized (1) various metal complexes having a novel optically active 1,1′-bi-2-naphthol derivative having various substituents introduced at the 6-position of a binaphthalene ring as a ligand. . (2) an optically active 1, having a substituent (substituted by an ester group or a vinyl group) at the 6-position of the binaphthalene ring;
By reacting a metal complex having a 1'-bi-2-naphthol derivative as a ligand with the amino group of a polymer having an amino group in the molecule, -NHC (= O)-or -NHCH
_A first polymer metal complex is obtained by forming a ₂ CH ₂ -bond or the like, and then a centralized metal is removed to obtain a polymerized optically active 1,1′-bi-2-naphthol derivative. Successfully obtained. (3) Further, a second polymer metal complex using the thus obtained polymer-supported optically active 1,1′-bi-2-naphthol derivative as a ligand was synthesized. (4) Furthermore, they have found that the obtained first and / or second polymer metal complexes are useful as asymmetric catalysts in asymmetric nitroaldol reactions and asymmetric Michael addition reactions.

That is, the present invention firstly provides the following general formula (1)

[0026]

Embedded image _{[Ma (Mb) x (L} 1 2-) y] (1)

In the formula, Ma and Mb each independently represent a metal atom, x represents 0, 1, 2, or 3, y represents 2 or 3, and L ₁ represents the following general formula ( 2)

[0028]

Embedded image

Wherein R is COR ¹ (r ¹ is a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _1-6 alkoxy group or a group represented by Nr ² r ³ And r ² ,
r ³ each independently represents a hydrogen atom or a C _1-6 alkyl group. Or Or ⁴ (r ⁴ represents a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _1-6 alkoxy group, or Cor ⁵ , and r ⁵ is a C _1-6 alkyl group , C _2-6 alkenyl group, C _1-6 alkoxy group.), And R ¹ , R ² , and R ³ each independently represent a hydrogen atom, a cyano group, a nitro group, a halogen atom,
_1-6 alkyl group, C _2-6 alkenyl group, C _1-6 alkoxy group, optionally substituted phenyl group or tri-C
_{Represents a 1-6} alkylsilylethynyl group, and n is 1 to 8
Represents an integer. The present invention provides a metal complex represented by｝.

In the metal complex represented by the general formula (1),
Ma is a Group III metal, a Group IV metal or a lanthanoid of the short-periodic table, and Mb is preferably an alkali metal. Also, the present invention provides, secondly, the following general formula (3)

[0031]

[Of 30] _{[Mc (Md) v (L} 2 2-) w] (3)

In the formula, Mc and Md each independently represent a metal atom, v represents 0, 1, 2, or 3, w represents 2 or 3, and L ₂ represents the following general formula ( 4)

[0033]

Embedded image

[Wherein (Poly) represents a polymer main chain having a primary amino group in the molecule, and A represents CO or-
Represents a group represented by CH ₂ CH ₂ C (＝ O) O—,
R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, a C _1-6 alkyl group,
It represents a C _2-6 alkenyl group, a C _1-6 alkoxy group, a phenyl group which may have a substituent or a tri-C _1-6 alkylsilylethynyl group, and n represents an integer of 1 to 8. ]｝
A metal complex represented by the formula:

In the second aspect, the Mc is:
It is preferably a group III metal, a group IV metal or a lanthanoid of the short-periodic periodic table, and Md is preferably an alkali metal.

The (Poly) is expressed by the following formula (5).

[0037]

Embedded image

(Wherein a represents an arbitrary natural number), a polystyrene derivative having a partial structure represented by the following formula in the molecule:
Alternatively, a dendrimer having an amino group in the molecule is preferable.

Thirdly, the present invention provides a method for producing a metal complex represented by the following general formula (3 '), which comprises the following steps (a) and (b):

(A) The following general formula (1 ')

[0041]

Embedded image _{[Ma '(Mb') x} '(L 1' 2-) y '] (1')

In the formula, Ma ′ represents the first metal, and Mb
Represents a second metal, x ′ represents 0, 1, 2, or 3, y ′ represents 2 or 3, and L ₁ ′ is represented by the following formula (2 ′)

[0043]

Embedded image

[Wherein, R ′ is Corr ¹ ′ (r ¹ ′ is a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group or a C _1-6
Represents a _1-6 alkoxy group. ) Or Or ⁴ ′ (r ⁴ ′
Represents a C _1-6 alkenyl group or Cor ^{5 ′} , wherein r ^{5 ′} is
Represents a _1-6 alkyl group, a C _1-6 alkenyl group, or a C _1-6 alkoxy group. ) ^{Represents, R 1 ', R 2'} , R 3 ' are each independently a hydrogen atom, a cyano group, a nitro group, a halogen atom, C _1-6 alkyl groups, C _2-6 alkenyl groups, C _{1 -6} alkoxy group, a phenyl group which may have a substituent or a tri-C _1-6 alkylsilylethynyl group, n 'is
Represents an integer of 1 to 8. The step of producing a metal complex represented by｝,

(B) a metal complex represented by the general formula (1 ') and a metal complex represented by the general formula (6)

[0046]

Embedded image

[Wherein (Poly) represents the same meaning as described above. Reacting a polymer having an amino group in the molecule represented by the following general formula (3 ′):

[0048]

Embedded image _{[Ma '(Mb') x} '(L 2' 2-) y '] (3')

In the formula, Ma ′, Mb ′, x ′, y ′ represent the same meaning as described above, and L ₂ ′ is represented by the following formula (4 ′)

[0050]

Embedded image

[Wherein (Poly) has the same meaning as described above, and R ⁴ ′, R ⁵ ′, and R ⁶ ′ each independently represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, _1-6 alkyl group, a C _2-6 alkenyl group, C _1-6 alkoxy group which may have a substituent phenyl group or a tri-C _1-6 alkylsilyl ethynyl group, n 'is 1 A ′ represents CO or —CH ₂ CH ₂ C (＝ O) O—
Represents a group represented by The present invention provides a method for producing a metal complex represented by｝.

In the third aspect of the present invention, Ma 'is preferably a Group III metal, a Group IV metal or a lanthanoid of the short period periodic table, and Mb' is preferably an alkali metal.

Fourthly, the present invention provides a method of the present invention wherein the compound represented by the general formula (3 ') is hydrolyzed (c) following the step (b). A) obtaining a 1,1′-bi-2-naphthol derivative represented by:

(D) 1, represented by the general formula (4 ')
Reacting a 1′-bi-2-naphthol derivative with a third metal compound and a fourth metal compound.

[0055]

[Of 38] _{[Mc '(Md') v} '(L 2' 2-) w '] (3 ")

(Wherein Mc ′ represents a third metal;
d ′ represents a fourth metal, L ₂ ′ represents a 1,1′-bi-2-naphthol derivative represented by the above formula (4 ′),
v ′ represents 0, 1, 2, or 3, w ′ represents 2 or 3. ) Is provided.

In the fourth aspect, the Mc ′
Is a Group III metal, a Group IV metal or a lanthanoid of the short-periodic table, and Md 'is preferably an alkali metal.

Fourth, the present invention provides a novel 1,1′-bi-2-naphthol derivative represented by the general formula (4).

In the fourth aspect, the above (P
(oli) is preferably a polystyrene derivative represented by the above formula (5) or a dendrimer having an amino group in the molecule.

Further, according to the present invention, sixthly, the following general formula (3)

[0061]

[Of 39] _{[Mc (Md) v (L} 2 2-) W] (3)

(Where Mc, Md, L ₂ , v and w are
Represents the same meaning as above. ) In the presence of the metal complex represented by the general formula (7)

[0063]

Embedded image R ⁷ CHO (7)

(Wherein R⁷Is a linear or branched C
_1-20Alkyl group, linear or branched C _1-20Alkenyl
Group, linear or branched C_1-20Alkynyl group, C_3-8Shi
Chloroalkyl group, phenyl group which may have a substituent
Or an aralkyl group which may have a substituent. )
An aldehyde compound represented by the general formula (8)

[0065]

Embedded image R ⁸ CH ₂ NO ₂ (8)

Wherein R ⁸ represents a hydrogen atom, a linear or branched C _1-20 alkyl group or a methylol group, and a nitroalkane represented by the following general formula: (9)

[0067]

Embedded image

(Wherein, R ⁷ and R ⁸ have the same meanings as described above, and C ^* represents an asymmetric carbon atom).

Also, the present invention provides, in a seventh aspect, the following general formula (3)

[0070]

[Of 43] _{[Mc (Md) v (L} 2 2-) w] (3)

(Where Mc, Md, L ₂ , v and w are
Represents the same meaning as above. ) In the presence of the metal complex represented by the general formula (10)

[0072]

Embedded image

[0073] (wherein, R ^9, R ¹⁰ each independently represents a linear or branched C _1-20 alkyl group. Further, by bonding R ⁹ and R ^10,. 5 to carbon atoms And an α, β-unsaturated ketone represented by the general formula (11):

[0074]

Embedded image CHR ¹¹ (CO ₂ R ¹² ) (CO ₂ R ¹³ ) (11)

(Wherein R¹¹Is a hydrogen atom or linear or
Is the branch C_1-20Represents an alkyl group. R ¹², R¹³Is it
Each independently represents a hydrogen atom, a linear or branched C_1-20A
Alkyl group, optionally substituted C_7-20Alkyl
Group or a phenyl group which may have a substituent
You. ) Reacting the compound represented by
General formula (12)

[0076]

Embedded image

Wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³
Represents the same meaning as described above, and C ^* represents an asymmetric carbon atom. ) Is provided.

[0078]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (1) A first invention is a metal complex represented by the following general formula (1).

[0079]

Embedded image _{[Ma (Mb) x (L} 1 2-) y] (1)

The metal complex represented by the general formula (1) is
It is a binuclear complex having two kinds of central metals, Ma and Mb. In the general formula (1), Ma and Mb each independently represent a metal element.

As Ma, for example, B, Al, Sc,
Ga, Y, In, Si, Ti, Ge, Zr, Sn, P
b, V, As, Nb, Sb, Ta, Bi, Cr, Se,
Mo, Te, W, Po, Mn, Tc, Re, At, F
e, Co, Ni, Ru, Rh, Pd, Os, Ir, P
t, La, Ce, Pr, Nd, Sm, Eu, Gd, T
b, Dy, Yb, Tl, Hf, Th, U and the like.

Of these, Ma is B, Al,
Group III metals such as Ga, In, etc.
Group IV metals of the short-periodic table such as i, Ge, Sn, etc. and La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, D
One or more elements selected from lanthanoids such as y, Pr and Yb are preferable.

Examples of Mb include alkali metals such as Li, Na and K and alkaline earth metals such as Be, Mg and Ca. Of these, alkali metals such as Li, Na, and K are preferable.

L ₁ is represented by the following general formula (2)

[0085]

Embedded image

In the general formula (2), n represents an integer of 1 to 8.
And R is COR¹[R¹Is a hydrogen atom, C_1-6Archi
Group, C_2-6Alkenyl group, C_1-6Alkoxy group or N
r^Twor ^Three(R^Two, R^ThreeAre each independently a hydrogen atom
Or C_1-6Represents an alkyl group. ) Represents a group represented by
You. ] Or Or^Four[R^FourIs a hydrogen atom, C_1-6Archi
Group, C_2-6Alkenyl group, C_1-6Alkoxy group, C
_7-12Aralkyl group, COR ^Five(R^FiveIs C_1-6Alkyl
Group, C_2-6Alkenyl group, C_1-6Table showing alkoxy groups
You. )].

In the above COR ¹ , r ¹ represents a hydrogen atom, a C _1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, n-pentyl, neopentyl, n-hexyl,

Vinyl, propenyl, isopropenyl, 1
- butenyl, 2-butenyl, 3-butenyl, butadienyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, C _2-6 alkenyl group such as 4-pentenyl group, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t A C _1-6 alkoxy group such as butoxy group,

A phenyl group which may have a substituent at any position of the benzene ring is shown. Examples of the substituent of the phenyl group include a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, and bromine; a C _1-6 alkyl group such as a methyl and ethyl group; and a C _1-6 alkoxy group such as a methoxy and ethoxy group. And the like. Further, the phenyl group may have a plurality of the same or different substituents.

R ² and r ³ each independently represent a hydrogen atom or C _1-6 such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, n-pentyl, neopentyl, n-hexyl, etc. Represents an alkyl group.

R ⁴ of Or ⁴ is a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, t-
Butyl, isobutyl, n-pentyl, neopentyl, n
-C _1-6 alkyl group such as hexyl group, vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3
-C _2-6 such as butenyl, butadienyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl and the like
Alkenyl group, methoxy, ethoxy, propoxy, isopropoxy, butoxy, C _1-6 alkoxy group such as t-butoxy group, or

A C _7-20 aralkyl group such as benzyl, α-methylbenzyl, phenethyl and the like, which may have a substituent at any position of the benzene ring.

Examples of the substituent on the benzene ring of the C _7-20 aralkyl group include a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, and bromine; a C _1-6 alkyl group such as a methyl and ethyl group; Examples thereof include a C _1-6 alkoxy group such as an ethoxy group. Further, the benzene ring may have a plurality of the same or different substituents.

As r ⁵ of the above-mentioned Cor ⁵ , methyl, ethyl, propyl, isopropyl, butyl, t-butyl,
C _1-6 alkyl group such as isobutyl, n-pentyl, neopentyl, n-hexyl group, vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, butadienyl, 1-pentenyl, 2-pentenyl,
3-pentenyl, 4-pentenyl C _2-6 alkenyl group such as, methoxy, ethoxy, propoxy, isopropoxy, butoxy, C _1-6 alkoxy C _1-6 alkyl group such as t- butoxy group, C _{2- 6} alkenyl groups and C _1-6 alkoxy groups.

[0095] More specific examples of groups represented by COR ¹ and Or ⁴ as COR ^1, for example, CO
CH ₃ , COCH ₂ H ₅ , COCH = CH ₂ , COP
h, COCH ₂ Ph, CO ₂ CH ₃ , CO ₂ C ₂ H ₅ ,
CO ₂ CH = CH ₂ , CO ₂ Ph, CO ₂ CH ₂ Ph,
_{CONH 2, CONHCH 3, CONHC 3} H 7 i, C
ON (CH ₃ ) _{2 and the} like.

Further, as Or ⁴ , OH, OCH ₃ , O
C ₂ H ₅ , OCH ₂ CH = CH ₂ , OCH ₂ Ph, OC
(= O) CH ₃ , OC (= O) C ₂ H ₅ , OC (= O)
Ph, OC (= O) CH = CH ₂ , O (= O) CH = C
HCH _{3 and the} like can be mentioned.

R ¹ , R ² and R ³ are each independently
A hydrogen atom, a cyano group, a nitro group, a halogen atom such as fluorine, chlorine, or bromine; a C _1- such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, n-pentyl, neopentyl, or n-hexyl group; ₆ alkyl group, vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, butadienyl, 1-
C _2-6 alkenyl group such as pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl group, C _1-6 alkoxy group C _1-6 such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy group Alkyl group, C
_2-6 alkenyl group, C _1-6 alkoxy group,

A phenyl group which may have a substituent at any position on the benzene ring, or a tri-C _1-6 alkylsilylethynyl group such as a trimethylsilylethynyl group. As the substituent of the phenyl group, a nitro group, a cyano group,
Halogen atoms such as fluorine, chlorine and bromine; C _1-6 alkyl groups such as methyl and ethyl groups; C atoms such as methoxy and ethoxy groups
Examples thereof _{include a 1-6} alkoxy group. Further, the phenyl group may have a plurality of the same or different substituents.

[0099] In the metal complex represented by the general formula (1), wherein L ₁ is, L ₁ in which two protons dissociated ^2-
In the form of a metal ion. Specifically, a metal complex having the following structure can be exemplified.

[0100]

Embedded image

(I) shows two BINOLs for one Ma.
A metal complex having a structure in which a ligand is coordinated and one Mb is further bonded, and (ii) shows two BINOs in one Ma
(Iii) a metal complex having a structure in which an L derivative is coordinated;
Is an example of a metal complex having a structure in which three BINOL derivatives are coordinated to one Ma, and three Mb are further bonded.
BINOL ligands are protons (H ⁺⁾ bonded to the metal at two dissociated divalent anion (L representing ₁ ² or L ₂ in ^2.).

The metal complex [type (iii)] in which three BINOL ligands are coordinated may have, for example, two types of conformers as shown in (iv). Are all included in the present invention.

(2) The second invention provides the following general formula (3)
Is a polymer metal complex represented by

[0104]

[Of 50] _{[Mc (Md) v (L} 2 2-) w] (3)

In the general formula (3), Mc and Md are
Each represents a metal atom corresponding to Ma and Mb.
Here, as the Mc, the third period of the short period type periodic table
Group metals, Group IV metals or lanthanoids are preferred, of which B, Si, Al and La are particularly preferred, and Md
Is preferably an alkali metal, and particularly preferably Li.

The ligand L ₂ is represented by the following formula (4):
It is an INOL derivative.

[0107]

Embedded image

In the formula (4), the polymer is not particularly limited as long as the metal complex represented by the general formula (1) can be immobilized in any form. There is no. In the present invention, as such a polymer, a polymer having an amino group in the molecule can be preferably used.

Examples of the polymer having an amino group in the molecule include an aminopolystyrene polymer obtained by reacting various amines, diamines or hydrazines with chloromethylated polystyrene, or an amino group in the molecule. And dendrimers having the same.

Chloromethylated polystyrene can be obtained as a commercial product (for example, commercially available from Wako Pure Chemical Industries, Ltd.), but can also be synthesized by, for example, chloromethylating polystyrene. . Incidentally, such polystyrene may be partially cross-linked by a cross-linking agent such as divinylbenzene,
Other additives may be contained.

When obtaining an aminopolystyrene polymer,
Examples of amines, diamines and hydrazines used include
If, NH_Three, CH_ThreeNH_Two, C_TwoH_FiveNH_Two, C_ThreeH₇
NH _Two, I-C_ThreeH₇NH_Two, C_FourH₉NH_Two, I-C
_FourH₉NH_Two, T-C_FourH₉NH_TwoEtc. C_1-6Alkyl
Amine, PhNH_TwoPhenylamine, C₆H_FiveCH
_TwoNH_TwoEtc. C_7-12Amines such as aralkylamines,

NH_TwoCH_TwoCH_TwoNH_Two, NH_TwoCH_Two
CH_TwoCH_TwoNH_Two, NH_TwoCH_TwoCH_TwoCH_TwoCH_Two
NH_Two, NH_TwoCH_TwoCH_TwoCH_TwoCH_TwoCH_TwoNH_Two
Etc. CH_ThreeNHCH_TwoCH_TwoNH_Two, CH_ThreeNHCH_Two
CH_TwoNHCH_Three, CH_ThreeNHCH_TwoCH_TwoCH_TwoNH
_Two, CH_ThreeNHCH_TwoCH_TwoCH_TwoCH_TwoNH_Two, CH
_ThreeNHCH_TwoCH_TwoCH_TwoCH_TwoCH_TwoNH_TwoNH_Twoetc
R¹¹NH (CH_Two)_lNHR¹²Diamine represented by
Kind, NH_TwoNH_Two, CH_ThreeNHNH_Two, C_TwoH_FiveNHN
H_Two, CH_ThreeNHNHCH _ThreeAnd hydrazines.
Can be

The dendrimer generally refers to a polymer having a structure in which another molecule is successively connected in a branched manner from the end of a certain molecule. In the present invention, the dendrimer having an amino group in the molecule (terminal) is used in the present invention. It is preferable to use For example, two propionic acids are bonded to the nitrogen atom of ethylenediamine, and further ethylenediamines are respectively bonded to the carbonyl portion of the propionic acid and amide bonds, and two more propionic acids are further bonded to the nitrogen atom of the terminal amino group of the ethylenediamine. There is an amino group-containing polymer obtained by repeating the bonding of an acid (for example, a polymer called “PAMAM Dendrimer” is known).

As such PAMAM dendrimers,
There are various things. For example, [-CH_TwoN (CH_TwoCH_TwoCONHCH_TwoCH_TwoN
H_Two)_Two]_Two, [-CH_TwoN [CH_TwoCH_TwoCONHCH_TwoCH_TwoN (CH_TwoCH_TwoCONHCH_TwoCH_TwoNH
_Two)_Two] _Two]_Two, [-CH_TwoN [CH_TwoCH_TwoCONHCH_TwoCH_TwoN [CH_TwoCH_TwoCONHCH_TwoCH_TwoN
(CH_TwoCH_TwoCONHCH_TwoCH_TwoNH_Two)_Two]_Two]_Two]_TwoEtc.
You. Of course, further polymerization is possible. They are,
It can also be obtained as a commercial product (for example, Cata
log Handbook of Fine Chem
icals (1996-1997) with Aldrich
See).

In L ₂ represented by the general formula (4), A serves as a bridge connecting the polymer having an amino group in the molecule and the BINOL derivative represented by the general formula (2). . That is, the BINOL derivative represented by the general formula (2) is fixed by A to an amino group portion of a polymer having an amino group in the molecule.

The A is not particularly limited as long as it is an amino group portion of a polymer having an amino group in the molecule and can fix the BINOL derivative represented by the general formula (2). . For example, the -NH-A- moiety in the general formula (4) is -NHCO- or -NH-CH
_{2 CH 2 C (= O)} O -, - N = CH -, - N = C (r
¹ )-and the like.

The 1,1-bi- ₂ of the above L ₁ and L 2
The naphthol ring may have the following two optical isomers (a) and (b). These are all included in the present invention. The same applies to L ₁ ′ and L ₂ ′ described later.

[0118]

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[0119] (3) Synthesis BINOL ligands L ₁ metal Synthesis of the complex (A) Synthesis of metal complex represented by the general formula (1) (a) L ₁ is, for example, be synthesized as follows be able to.

[0120]

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BINOL derivatives represented by the general formula (13) are described in Bayston, D .; J. Fraser, J .;
L. Ashton M .; R. Baxter, A .;
D. Polywka, E .; C. Moses, E .; ,
J. Org. Chem. , 63 , 3137 (199
8). Can be produced according to the method described in

Various derivatives can be produced using the obtained compound (13) as a starting material. The general formula (1
Of the compounds represented by 4), Q is Nr ² r ³ (r ² ,
r ³ has the same meaning as described above. For example, the compound represented by the general formula (13) is obtained by hydrolyzing a compound represented by the general formula (13) to form a carboxylic acid, and then forming an acid halide with a halogenating agent such as thionyl chloride, thionyl bromide, oxalyl chloride, and sulfuryl chloride. , Ammonia, and various amines.

Of the compounds represented by the general formula (14),
The compound (14-1) in which Q is CH ₂ OH can be obtained by reducing the compound represented by the general formula (13) using a reducing agent such as LiAlH ₄ . Solvents that can be used in this reaction include ether solvents such as tetrahydrofuran (THF) and diethyl ether.

Various CH ₂ Or ⁴ forms (14-2) can be derived from the obtained CH ₂ OH form (14-1) as a starting material (see the following reaction formula).

[0125]

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Further, among the compounds represented by the general formula (14), Q represents CH ₂ Or ⁴ [r ⁴ represents COR ⁵ (r ⁵ represents C _1-6 alkyl)]. Is a compound
For example, it can be produced by reacting a compound in which B is CH ₂ OH with various acid halides and acid anhydrides in the presence of a base.

As a base which can be used in this reaction, triethylamine, pyridine and the like can be mentioned. Examples of the acid halide include acetyl chloride, propionyl chloride, benzoyl chloride, and acrylic acid chloride. Examples of the acid anhydride include acetic anhydride and benzoic anhydride.

Among the compounds represented by the general formula (14),
Q is CH ₂ Or ⁴ (r ⁴ is a C _1-6 alkyl group or C
Represents a _1-6 alkenyl group. ) Is, for example,
In the presence of a base such as triethylamine, pyridine, sodium carbonate, potassium carbonate, or potassium t-butoxide, dimethyl sulfate, diethyl sulfate, methyl iodide, ethyl iodide, and bromide are added to the compound represented by the general formula (13). It can be produced by the action of an alkylating agent such as propyl or isopropyl iodide.

Of the compounds represented by the general formula (14),
Q is CH_TwoOr^Four(R^FourIs COR ^Five(R^FiveIs C_1-6A
Represents a lucoxy group. A) is, for example,
After hydrolyzing the compound represented by the formula (13),
Alternatively, in the presence of a base catalyst, an alcohol (r^FourOH)
A method of acting a compound represented by the general formula (13)
After hydrolysis, a halogenating agent such as thionyl chloride is made.
To an acid halide, and in the presence of a base, an alcohol
(R^FourOH) or the general formula (1)
The compound represented by 3) is converted to an alcohol (r^FourOH)
In the presence of a catalyst such as titanium alkoxide, the ester
It can be produced by a method of performing an exchange reaction or the like.

(B) Production of Metal Complex The metal complex represented by the general formula (1) can be produced, for example, as follows.

[0131]

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That is, an organic solvent solution of a metal compound of Ma and an organic solvent solution of L ₁ are mixed, and an organic solvent solution of a metal compound of Mb is added. And manufacture.

As the metal compound of Ma, organic metals, metal alkoxides, metal halides, metal hydrides and the like can be used.

As the organic metal, for example, Al (C
Organic aluminum such as H ₃ ) ₃ and Ga (CH ₃ ) ₃ and organic gallium can be used.

As the metal alkoxide, for example, La
_{(O-i-Pr) 3} , La 3 (OBu t) 9, lanthanides etc. _{^{alkoxide, Ti (O- i Pr) 4}} , Zr
Metal alkoxides such as alkoxides of transition metals such as (OC ₂ H ₅ ) ₄ can be mentioned.

As the metal halide, for example, YC
l ₃ , LaCl ₃ , NdCl ₃ , SmCl ₃ , EuCl
_{3, GdCl 3, TbCl 3,} YbCl 3, SiC
l ₄ , SnCl ₄ , AlCl ₃ , FeCl ₃ , TiCl
₄ , CoCl _{2 and the} like, and hydrates thereof.

Examples of the metal hydride include L
iAlH ₄ , (Et) ₂ AlH, (i-Pr) ₂ Al
H, (i-Bu) ₂ AlH, BH ₃ , B ₂ H ₆ , CaH
₂ , NaH, KH and the like.

The addition amount of the metal compound of Ma depends on the amount of the ligand L ₁
It is preferably about 0.1 to 3 equivalents to 1 molar equivalent.

As the organic solvent that can be used in the reaction, any solvent can be used without particular limitation as long as it can dissolve the metal compound and L ₁ and is inert. For example, TH
Ether solvents such as F, diethyl ether, dioxane, 1,2-dimethoxyethane, halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, monochlorobenzene, benzene, toluene, xylene, n-pentane, n-hexane, n-
Hydrocarbon solvents such as heptane, fatty acid esters such as ethyl acetate and butyl acetate, dimethyl sulfoxide, N, N
-Dimethylformamide (DMF) and the like, and hydrated solvents thereof.

As the metal compound Mb, an alkali metal compound is preferably used. Examples of the alkali metal compound include CH ₃ Li, n-BuLi, and (CH ₃ )
Organic lithium such as ₃ CLi, LiOH, NaOH, KO
H and the like are alkali metal hydroxides, alkali metals such as Na, K and Li, alkaline earth metals such as Mg, NaOCH ₃ ,
Alkoxides of alkali metals such as NaOC ₂ H ₅ and KO (t-Bu), alkoxides of alkaline earth metals such as Mg (OC ₂ H ₅ ) ₂ , and LiAlH ₄ can be used.

The addition amount of the metal compound of Mb depends on the amount of the ligand L ₁
Is preferably about 0.1 to 3 equivalents to 1 mol equivalent of the above.

The reaction proceeds smoothly in a temperature range from -100 ° C. to the boiling point of the solvent used, and the desired metal complex can be isolated by a usual post-treatment operation. In some cases, the metal complex can be stored in the state of a reaction solution, or can be used as it is as an asymmetric reaction catalyst in the state of a reaction solution.

(C) Production of Polymer Metal Complex The polymer metal complex of the present invention can be produced, for example, as follows. (I) Production of metal complex (1 ″)

[0144]

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(Wherein, R ⁴ , R ⁵ and R ⁶ have the same meanings as described above, and Ma ″ is a third metal, for example, a Group III metal or a Group IV metal of the short-periodic periodic table) Or Mb ″ represents a fourth metal, for example, an alkali metal, and L ₁ ′ is L ₁ of which R ′ is CO ₂ r ′.
(R ′ represents a hydrogen atom or a C _1-3 alkyl group) or a BINOL derivative in which OCOCH ＝ CH ₂ ,
x "and y" each independently represent an integer of 1 to 3. )

(Ii) Production of polymer metal complex (3 ′) Then, the metal complex (1 ″) is reacted with a polymer having an amino group in the molecule to obtain a compound represented by the general formula (3 ′). To obtain a high-molecular metal complex.

That is, when L ₁ ′ is R ′ and CO ₂ r ′
In the case of the compound (r ′ represents a lower alkyl group), a polymer represented by the general formula (5) is added to an organic solvent solution of the metal complex (1 ″), and By heating and stirring in the presence of a base according to
L ₂ supported on the polymer can be obtained by the (＝ O)-bond. When L ₁ ′ is a carboxylic acid, it can also be produced by reacting with a polymer represented by the general formula (5) in the presence of a dehydrating agent such as DCC.

In the above L ₁ ′, R ′ is OCOCH
In the case of a compound in which 2CH ₂ , a polymer represented by the general formula (5) is added to an organic solvent solution of the metal complex (1 ″), and the polymer is heated from −10 ° C. to the boiling point of the solvent used. -NHCH ₂ C
L ₂ ′ supported on the polymer can be obtained by the H ₂ C (＝ O) O— bond.

Solvents that can be used in these reactions include, for example, ether solvents such as THF, diethyl ether, dioxane and 1,2-dimethoxyethane, methylene chloride, chloroform, carbon tetrachloride, 1,1,1 −
Halogen solvents such as trichloroethane and monochlorobenzene, benzene, toluene, xylene, n-pentane,
Hydrocarbon solvents such as n-hexane and n-heptane; fatty acid esters such as ethyl acetate and butyl acetate; dimethyl sulfoxide; N, N-dimethylformamide (DMF)
And the like.

(Iii) Production of L ₂ 'Next, the resulting high-molecular metal complex represented by the general formula (3') is subjected to acid hydrolysis to remove the central metal, thereby obtaining L ₂ '.
You can get ₂ '.

In this oxidative hydrolysis, for example, an aqueous solution of a mineral acid such as hydrochloric acid, nitric acid or sulfuric acid is added to the solution (or suspension) of the polymer metal complex (3 ′), It is performed by stirring in a temperature range.

(Iv) Production of polymer metal complex (3 ″) Finally, using the obtained L ₂ ′, a polymer metal complex (3 ″) can be produced. That is, the organic solution or suspension of the organic solvent L _2, 'and an organic solvent solution of the compound, the L ₂ third metal (Mc)' and an organic solvent solution of (or suspension) were mixed, Next, it can be produced by adding an organic solvent solution of a fourth metal (Md ′) compound.

[0153]

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Here, Mc ′, Md ′ and L ₂ ′ represent the same meaning as described above, and v ′ represents 0, 1, 2 or 3.
w ′ represents 2 or 3. The metal compounds of Mc 'include BH ₃ , B ₂ H ₆ , Al
(CH ₃ ) ₃ , SiCl ₄ , La (Oi-Pr) ₃ ,
La ₃ (OBu ^t ) ₉ , LaCl ₃ (or its hydrate)
And the metal compound of Md ′ is n-BuL
i, sec-BuLi, t-BuLi, and the like, respectively. Further, as other, LiAlH
₄ , (Et) ₂ AlH, (i-Pr) ₂ AlH, (i-
Bu) ₂ AlH or the like can also be used.

As the organic solvent that can be used for the reaction, any solvent can be used without particular limitation as long as it can dissolve the third and fourth metal compounds and L ₁ ′ and is inert. For example, THF, diethyl ether, dioxane,
Ether solvents such as 1,2-dimethoxyethane, methylene chloride, chloroform, carbon tetrachloride, halogen solvents such as 1,1,1-trichloroethane, monochlorobenzene, benzene, toluene, xylene, n-pentane,
Hydrocarbon solvents such as n-hexane and n-heptane; fatty acid esters such as ethyl acetate and butyl acetate; dimethyl sulfoxide; N, N-dimethylformamide (DMF)
And hydrated solvents.

In this production method, a metal complex (1 ″) in a state before being bonded to a polymer is formed in advance, and then the metal complex (1 ″) is reacted with the polymer to form a dummy metal Ma ′. And a polymer metal complex (3 ′) having Mb ′ and Mb ′, and further converting the central metals Ma ′ and Mb ′ to another metal M
The polymer metal complex (3 ″) is obtained by exchanging the complex with c ′ and Md ′. When the metal complex (1 ″) is the final target, the above-mentioned step of exchanging the central metal is carried out. It becomes unnecessary.

According to this method, a plurality of polymer BINO
It is possible to form a polymer having a three-dimensional structure in which a space for binding the hydroxyl group of the L ligand (L ₂ ′) and the central metal is secured. That is, the central metals Ma ′ and Mb ′ of the metal complex (1 ″) are formed by a plurality of polymers B formed.
It serves as a dummy atom for forming the INOL ligand (L ₂ ′) to have a three-dimensional structure capable of bonding to the central metal.

The polymer metal complex represented by the general formula (3 ″) can be prepared by directly forming the polymer BINOL ligand without forming the metal complex (1 ″) as shown in the following reaction formula. L ₂ '), followed by Mc' and Md '
It is also possible to add the metal compound of the above. However, in this case, the central metal is a plurality of polymers BINOL.
It is necessary to synthesize a polymer BINOL ligand having a three-dimensional structure capable of binding to the hydroxyl group of the ligand (L ₂ ′) by any method.

[0159]

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Formula (3), (3 ') or (3 ")
The metal complex represented by the general formula (1), (1 ′) or
As with the metal complex represented by (1 ″) (see Chemical formula 49), gold
Genera (Mc, Mc'Md, Md ') and L_Two(L_Two’)
The bonding molar ratio varies depending on the type of metal. example
If Mc (Mc ') is a lanthanoid such as La or Al
Yes, when Md (Md ') is an alkali metal such as Li
Is 3 moles of L with respect to 1 mole of Mc (Mc ').
_Two(L_Two') And 3 moles of Md (Md') are bonded.
If Mc (or Mc ') is boron (B) or aluminum (A
l) wherein Md (or Md ') is an alkali gold such as Li
Genus, 2 mol per 1 mol of Mc (Mc ') a
Mole L_Two(L_Two') And 1 mol of Md (Md')
I do. When Mc (Mc ') is silicon (Si),
Is 2 moles of L per mole of silicon._Two(L _Two'))But
The respective bound metal complexes are obtained.

General formulas (1), (1 '), (1 ") and (3)
The reaction for synthesizing the metal complex represented by (3 ′) and (3 ″) proceeds smoothly in a temperature range from −100 ° C. to the boiling point of the solvent to be used, and the target metal is subjected to ordinary post-treatment operations. The complex can be isolated, and in some cases, the metal complex can be stored in the form of a reaction solution (or suspension), or can be directly used as an asymmetric reaction catalyst in the state of a reaction solution. it can.

The structure of these metal complexes was determined by elemental analysis, X
Line crystal analysis, optical rotation measurement, IR spectrum, ¹ H-NM
R spectrum, UV absorption spectrum, visible light absorption spectrum, mass spectrum, CD (Circular D)
It can be determined by measuring various spectra such as ichroism spectra.

The general formula (2) which can be produced and
BINOL derivative (L) represented by (4)₁And L_Two)of
Examples are shown in Tables 1 and 2 below. In Table 2,
STY (* 1) is a police represented by the general formula (5).
Represents a Tylene derivative, and Dend is [-CH_TwoN (CH_TwoCH_TwoCONHC
H_TwoCH_TwoNH_Two)_Two]_Two, [-CH_TwoN [CH_TwoCH_TwoCONHCH_TwoCH_TwoN (CH_TwoCH_TwoCONHCH
_TwoCH_TwoNH_Two)_Two]_Two]_Two, [-CH_TwoN [CH_TwoCH_TwoCONHCH_TwoCH_TwoN [CH_TwoCH_TwoCONHC
H_TwoCH_TwoN (CH_TwoCH_TwoCONHCH_TwoCH _TwoNH_Two)_Two]_Two]_Two]_TwoEtc.
One or more PAMAM dendrimers
(Each NH_TwoBond at the base).

[0164]

[Table 101]

[0165]

[Table 102]

[0166]

[Table 201]

[0167]

[Table 202]

[0168]

[Table 203]

[0169]

[Table 204]

Examples of the metal complexes represented by the general formulas (1) and (3) which can be produced as described above are shown in Tables 3 and 4 below. In the table, L ₁ -1
Represents the compound of Compound No. 1-18 in Table 1 as L
₁ -2, wherein the in Table 1, the compound of Compound No. 1-22 in Table, L ₂ -1 during the second table, Compound No. 2
L ₂ -2 represents the compound of Compound No. 2-12 in Table 2 above.

[0171]

[Table 301]

[0172]

[Table 401]

(4) Production of asymmetric nitro alcohol The polymer catalyst represented by the general formula (3) has excellent asymmetric catalytic activity in the nitro aldol reaction as shown below.

[0174]

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(In the formula, C ^* represents an asymmetric carbon atom.) In this reaction, the aldehyde 1 represented by the general formula (7) is used.
0.5 to 2 molar equivalents of the general formula (8) based on the molar equivalents
Is carried out at a reaction temperature of about -100 ° C to 100 ° C in the presence of 0.001 to 1 molar equivalent of the metal complex represented by the general formula (3), thereby obtaining a compound represented by the general formula ( An optically active nitro alcohol represented by 9) is obtained. The compound represented by the general formula (9) may have four types of optical isomers. According to the present invention, any one of these isomers may be selectively obtained. Can be. Which kind of optical isomer is formed preferentially is determined by the absolute configuration of the metal complex catalyst used.

In the general formula (7), R ⁷ is methyl,
Ethyl, propyl, isopropyl, butyl, pentyl,
A straight-chain or branched C _1-20 alkyl group such as hexyl, heptyl, octyl, nonyl, decyl, dodecyl group, and a straight-chain or branched C _1-20 alkenyl group such as propenyl and crotyl group, and a straight chain such as propynyl group. or branched C _{1- 20}
Alkynyl, cyclopropyl, cyclopentyl, C _{3- 8} cycloalkyl groups such as cyclohexyl group, which may have a substituent phenyl group, or benzyl, alpha-methylbenzyl, have a substituent such as a phenethyl group Represents an aralkyl group which may be substituted.

As the aldehyde represented by the general formula (7), more specifically, for example, formaldehyde, acetaldehyde, propionaldehyde, isopropylaldehyde, n-butyraldehyde, cyclohexylaldehyde, peropenylacetaldehyde, crotonaldehyde, benzaldehyde Aldehyde, cinnamic aldehyde and the like.

In the general formula (8), R ⁸ represents a hydrogen atom, a linear or branched C ₁ such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or dodecyl group. _-20
Represents an alkyl group or a methylol group.

As the nitroalkane represented by the general formula (8), more specifically, for example, nitromethane, nitroethane, nitropropane, nitrobutane, nitroethanol and the like can be mentioned.

The solvent used in this reaction is not particularly limited as long as it dissolves the raw materials aldehyde (7) and nitroalkane (8) and does not react with them. For example, water, alcohol solvents such as methanol, ethanol, propanol and ethylene glycol, ether solvents such as diethyl ether, THF, 1,4-dioxane and 1,3-dimethoxypropane, methylene chloride,
Halogen solvents such as chloroform, carbon tetrachloride, chlorobenzene and dichlorobenzene, hydrocarbon solvents such as pentane, hexane, cyclohexane, benzene, toluene and xylene, fatty acid esters such as ethyl acetate and butyl acetate, dimethyl sulfoxide, N, N -Dimethylformamide or the like, or a mixed solvent of two or more thereof can be used.

In this reaction, by further adding an alkali metal compound to the reaction system, the reaction time can be shortened, and the reaction yield and the optical yield can be increased in some cases. Examples of alkali metal compounds that can be added include alkyl alkali metals such as methyl lithium and t-butyl lithium, and alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide. The amount of the alkali metal compound to be added is about 0.01 to 10 molar equivalents per 1 molar equivalent of the metal complex represented by the general formula (3).

After terminating the reaction by adding a reaction terminating agent such as dilute hydrochloric acid or an aqueous solution of ammonium chloride to the reaction system, the metal complex represented by the general formula (3) is removed from the reaction system, and then the reaction is stopped. An object can be obtained by the processing operation. Since the metal complex represented by the general formula (3) is a polymer metal complex, it can be easily removed from the reaction system,
Further, the BINOL derivative can be reused.

In the optically active nitro alcohol obtained, when a compound in which R ⁸ is a hydrogen atom in the above R ⁸ CH ₂ NO ₂ is used, the carbon to which the hydroxyl group is bonded becomes an asymmetric carbon atom, and R ⁸ is When a compound other than a hydrogen atom is used, the carbon to which the hydroxyl group is bonded and the carbon atom to which the nitro group is bonded are asymmetric carbon atoms. Therefore, when reacting nitromethane to obtain nitro alcohol, two kinds of optical isomers are used. When reacting a compound in which R ⁸ is a C _1-20 alkyl group, for example, nitroethane or the like, four kinds of optical isomers are used. Optical isomers may form.

When the metal complex represented by the above general formula (3) of the present invention is used as an asymmetric catalyst, any of these optical isomers can be preferentially obtained. . The configuration of the nitro alcohol that can be obtained depends on the configuration of the metal complex used.

Examples of the nitro alcohol obtained as described above are shown in Table 5 below. In Table 5, * indicates the position of the asymmetric carbon atom, and its absolute configuration is represented by (R) or (S).

[0186]

[Table 501]

From the obtained optically active nitro alcohol,
By converting a nitro group into an amino group, a carboxyl group, a hydroxyl group, or the like, a useful drug or the like can be produced. For example, by a reduction reaction using a general catalytic hydrogenation catalyst such as PtO ₂ or Pd—C, it can be converted to an optically active amino alcohol while maintaining the original configuration.

(5) Production of Optically Active Michael Adduct The polymer catalyst represented by the general formula (3) has an excellent asymmetric catalytic activity in the Michael (addition) reaction as shown below.

[0189]

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(In the formula, C ^* represents an asymmetric carbon atom.) In this reaction, the α, β-unsaturated ketone represented by the general formula (10) is reacted with the α, β-unsaturated ketone. 0.5 to 2 molar equivalents of the compound represented by the general formula (11) and 0.001 to 1 molar equivalents of the metal complex represented by the general formula (3) per 1 molar equivalent Below, the reaction temperature -10
By performing at about 0 ° C. to 100 ° C., general formula (12)
To obtain an optically active Michael adduct represented by
Either optical isomer can be selectively obtained.

In the compound represented by formula (10), R ⁹ and R ¹⁰ are each independently methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Represents a linear or branched (optionally substituted) C _1-20 alkyl group such as a dodecyl group. R ⁶ and R ⁷ may combine to form a carbon chain having 5 to 8 carbon atoms, such as a cyclopentane, cyclohexane, or cyclooctane ring.

As the substituent for the C _1-20 alkyl group,
For example, a C _1-6 alkoxy group such as a cyano group, a nitro group, a methoxy, an ethoxy, a propoxy, an isopropoxy group,
C _1-6 alkylthio group such as methylthio, ethylthio group, etc.
Halogen atoms such as fluorine, chlorine and bromine; C _1-6 alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups; phenyl, 4-chlorophenyl, 4-methylphenyl, 3-cyanophenyl, 2-methoxyphenyl, 3,4 And a phenyl group which may have a substituent such as a dichlorophenyl group.

More specific examples of the compound represented by formula (10) include propenyl methyl ketone, 1-
Propenyl methyl ketone, 1-butenyl methyl ketone,
Examples thereof include 2-phenyl-1-propenylmethyl ketone, cyclopentenone, cyclohexenone, and the like.

In the compound represented by the general formula (11), R ¹¹ represents a hydrogen atom or a methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl group or the like. Represents a linear or branched C _1-20 alkyl group,

R ¹² and R ¹³ each independently represent a hydrogen atom, a straight-chain or branched C such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or dodecyl group. _1-20
Alkyl group, benzyl, α-methylbenzyl, α, α-
_C7-20 aralkyl group which may have a substituent such as dimethylbenzyl or phenethyl group, methoxy, ethoxy, propoxy, isopropoxy, butoxy, linear or branched _C1-20 alkoxy such as t-butoxy group. Represents a phenyl group which may have a group or a substituent.

Examples of the substituent of the C _7-20 aralkyl group which may have a substituent and the phenyl group which may have a substituent include a hydroxyl group, a cyano group, a nitro group, a fluorine atom,
Halogen atoms such as chlorine and bromine, and C atoms such as methyl and ethyl groups
_1-6 alkyl group, methoxy, C _1-6 alkoxy group such as ethoxy group, methoxycarbonyl, and the like C _1-6 alkoxycarbonyl group such as ethoxycarbonyl group. In addition, these substituents are substituted at any position of the benzene ring, and the same or different plural groups may be substituted.

Specific examples of the compound represented by the general formula (11) include, for example, malonic acid, monomethyl malonate (half ester), monoethyl malonate, dimethyl malonate, diethyl malonate, diisopropyl malonate. Malonic acid and malonic acid derivatives, such as t-butyl methyl malonate, dibutyl malonate, dibenzyl malonate, dimethyl methyl malonate, diethyl methyl malonate, diisopropyl methyl malonate, dibenzyl methyl malonate,

Acetylacetone, benzoylacetone,
Propionylacetone, 1,1,1-trifluoroacetylacetone, 1,1,1,5,5,5-hexafluoroacetylacetone, 1-phenylpentane-2,4-
Dione, 1,5-diphenylpentane-2,4-dione, 1-cyclopropylbutane-1,3-dione, 1-
Β-diketones such as cyclopentylbutane-1,3-dione, 1-cyclohexylbutane-1,3-dione,

Β-keto acid derivatives such as acetoacetic acid, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, isopropyl acetoacetate, butyl acetoacetate, methyl benzoylacetate, ethyl benzoylacetate, methyl methylacetoacetate, and methyl ethylacetoacetate. No.

After terminating the reaction by adding a reaction terminator such as an acid such as dilute hydrochloric acid or an aqueous solution of ammonium chloride to the reaction system, the metal complex represented by the general formula (3) is removed from the reaction system. The target product can be obtained by ordinary post-processing operations. The metal complex represented by the general formula (3) is
Since it is a polymer metal complex, it can be easily removed from the reaction system, and the BINOL derivative can be reused.

Optically Active Michael Adduct (12) Obtained
Has two asymmetric carbon atoms in the molecule. Therefore, 4
There may be different optical isomers. In the present invention, any of these optical isomers can be preferentially obtained. The configuration of the Michael adduct that can be obtained is determined by the configuration of the metal complex represented by the general formula (3).

Table 6 below shows examples of the optically active Michael adduct (12) obtained as described above. In Table 6, * indicates the position of two asymmetric carbon atoms, and these asymmetric carbon atoms are indicated by (R) and (S) in absolute configuration. , (S, R), (R, S),
(R, R).

[0203]

[Table 601]

[0204]

[Table 602]

[0205]

[Table 603]

[0206]

The present invention will be described in more detail with reference to the following examples. Example 1 Preparation of BINOL Derivative 1 Bayston, D .; J. , Fraser J .; L. ,
Ashton M. R. , Baxter A .; D. , P
olywka, E .; C. , Moses E .; , J. et al. Or
g. Chem. , 63 , 3137 (1998). (R) -BINOL derivative was synthesized using (R) -BINOL (15) as a starting material according to the method described in (1).

[0207]

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Example 2 {Al (Li) ₃ [(BINO)
^{Preparation of} L derivative 1) ^2- ] ₃ ｝

[0209]

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(R) -BINOL derivative (15) 120
mg (0.3 mmol) was dissolved in anhydrous THF (3.0 ml), and trimethylaluminum (AlMe ₃ ) was added under ice-cooling.
98 μl of n-hexane solution (1.02 M, 0.1 mm
ol), and then n-BuLi n
-Hexane solution 195 μl (1.53 M, 0.3 mmol
The title metal complex was prepared by adding l).

¹³ C-NMR (THF, dppn) of {Al (Li) ₃ [(BINOL derivative 1) ^2- ] ₃ }: 17
2.02, 161.36, 160.89, 137.47, 134.37, 133.45, 132.
89, 128.76, 128.00, 127.51, 127.28, 126.95, 126.4
7, 126.13, 125.96, 125.14, 123.69, 120.35, 120.0
4,119.76

Example 3 {Al (Li) ₃ [(BINO
Production of L derivative 2) ^2- ] ₃ ｝

[0213]

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｛Al (Li) obtained in Example 2
_3. [(BINOL Derivative 1) ^2- ] ₃ } THF solution
In 0 ml, an aminostyrene polymer represented by the general formula (17) (hereinafter referred to as “PS-amine”;
a 'represents a natural number. ) 2.0, and the mixture was heated and refluxed at 70 ° C. for 3 hours to obtain a target THF-solution of the polymer-supported metal complex (18).

The IR spectrum of the metal complex (18) (nu
jol): 1661 cm ^-1 (carbonyl of amide)

Note that PS-amine (17) is a commercially available product (manufactured by Wako Pure Chemical Industries, Ltd., Cl content: 0.8 mmol / l).
g, 100-200 mesh, catalog No.
038-09524) is heated to reflux in butanediamine in the presence of potassium carbonate, and the resulting crude product is treated with THF → H ₂ O → EtO
The product obtained by washing in the order of H → THF → Et ₂ O was used. The terminal content of the obtained PS-amine (17) is as follows:
ca. 0.76 mmol / g.

Example 4 Production of BINOL Derivative 2

[0218]

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ΔAl (Li) obtained in Example 3
₃ [(BINOL derivative 2) ^2- ] _{3 3} (18) in THF
The metal-oxygen bond was cleaved by adding 2 ml of 1N HCl at 0 ° C. to the solution. The precipitate was collected by filtration, washed twice with 3 ml of water, twice with 3 ml of THF, and twice with 3 ml of diethyl ether, and dried under reduced pressure at room temperature for 3 hours to obtain 2.3 g of the desired product (19). . Yield: ca.
57% (the yield is based on the recovered BINOL derivative (15)
Was calculated based on the amount of )

Polymer [(19), BINOL derivative 2]
IR spectrum (nujol) of 3200 cm ^-1 (p
henol OH)

Example 5 {La (Li) ₃ [(BINO)
Production of L derivative 2) ^2- ] ₃ ｝

[0222]

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The BINOL derivative (1) obtained in Example 4
9) 2.3 g (ca. 0.074 mmol / g) were suspended in ₃ ml of anhydrous THF, and at 0 ° C., 500 μl of a solution of La (OPr ⁱ ) ₃ in THF (0.1 M, 0.05 mmol) was added.
l), 98 µl of nBuLi n-hexane solution (1.5
3M, 0.150 mmol) and water in THF 100
μl (0.5 M, 0.05 mmol) are added in this order,
{La (Li) ₃ [(BINOL derivative 2) ^2- ] ₃ }
(20) was obtained.

Example 6 Production of {BLi [(BINOL Derivative 1) ^2- ] ₂ }

[0225]

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(R) -BINOL derivative (15) 80 m
g (0.2 mmol) was dissolved in 2.0 ml of anhydrous THF, and 100 μl (1.0 ml) of a THF solution of BH ₃ was added under ice-cooling.
0M, 0.1 mmol) and then at the same temperature,
130 μl of nBuLi n-hexane solution (1.53
M, 0.2 mmol) to prepare a THF solution of the title complex (21). This was used for the next reaction without isolation.

Example 7 Production of {BLi [(BINOL Derivative 3) ^2- ] ₂ }

[0228]

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The ２９BLi [(BINO) obtained in Example 6
L derivative 1) ^2- ] ₂ ^2- (21) in 2.0 ml of THF solution
2.0 g of PS-amine was added to
By heating and refluxing for an hour, a THF solution of the title complex was prepared. This was used for the next reaction without isolation.

IR spectrum (nujol) of {BLi [(BINOL derivative 3) ^2- ] ₂ }: 159
8 cm ^-1 (carbonyl of amide)

Example 8 Production of BINOL Derivative 3

[0232]

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The ３３BLi [(BINO) obtained in Example 7
The metal-oxygen bond was cleaved by adding 2 ml of 1N HCl at 0 ° C. to the THF solution of L derivative 3) ²⁻ ) ₂ ｝ (22) in the same manner as in Example 3. The precipitate is collected by filtration,
This was washed twice with 3 ml of water, twice with 3 ml of THF, and twice with 3 ml of diethyl ether, and dried under reduced pressure at room temperature for 3 hours to obtain 2.1 g of the desired product (23). yield:
ca. 63% (The yield was calculated based on the amount of the recovered BINOL derivative (15).)

Polymer [(23), BINOL derivative 3]
IR spectrum (nujol) of 3190 cm ^-1 (p
henol OH)

Example 9 Production of {AlLi [(BINOL Derivative 3) ^2- ] ₂ }

[0236]

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The BINOL derivative 3 obtained in Example 8
2.1 g of (23) was suspended in 3.0 ml of anhydrous THF, and 49 μl of a solution of AlMe ₃ in n-hexane at 0 ° C.
(1.02 M, 0.05 mmol), and n-BuLi
33 μl of n-hexane solution (1.53 M, 0.05 m
mol)) in this order to give the title AlLi complex (24).

Example 10 Catalytic Asymmetric Nitroaldol Reaction

[0239]

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ΔLa (Li) obtained in Example 5
₃ [(BINOL derivative 2) ^2- ] ₃ ｝ (20) in THF
Suspension (ca. 10 mol% based on the substrate)
Is cooled to −40 ° C. and 270 μm of nitromethane (26)
l (5 mmol) and hydrocinnamaldehyde (2
5) 66 μl (0.5 mmol) was added, and the mixture was stirred at −40 ° C. for 65 hours. Thereafter, 2 ml of 1N-HCl was added to stop the reaction, the solid layer was separated by filtration, and the solid layer was washed with ethyl acetate 1
After washing three times with 0 ml, the ethyl acetate solution was collected, combined with the filtrate, dried over anhydrous sodium sulfate and concentrated. The concentrate was subjected to flash column chromatography (acetone /
Purification with hexane = 1/9) afforded 59.4 mg of the desired product, nitroalcohol (27) (61% yield).
This was purified with an optical resolution column (Daicel Co., Ltd., trade name: CHIRAPAK AD, eluent: hexane / isopropyl alcohol = 9/1, elution rate = 1.0 ml /
(min, detection wavelength = 254 nm). As a result, it was found that the optical purity of the obtained nitro alcohol (27) was 37% ee.

Example 11 Catalytic Asymmetric Michael Reaction

[0242]

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The ｛AlLi [(BIN) obtained in Example 9
OL derivative 3) ^2- ] ₂ } (24) in a THF suspension (ca. 10 mol% with respect to the substrate) was added at room temperature to 125 μl (0.5) of dibenzyl malonate (29) at room temperature.
mmol) and 48 μl of cyclohexenone (28)
(0.5 mmol) and stirred at room temperature for 44 hours.
Thereafter, 2 ml of 1N HCl was added to the reaction solution to stop the reaction, the solid layer was separated by filtration, and the solid layer was washed with 10 ml of ethyl acetate.
Washed twice. The ethyl acetate solution was collected, dried over anhydrous sodium sulfate, and concentrated. Flash column chromatography of the concentrate (acetone / hexane = 1/9)
And the desired Michael adduct (30) was
44.7 mg were obtained. Yield 48%.

This was purified by using an optical resolution column (Daicel Co., Ltd., trade name: CHIRAPAKAD, eluent: hexane / isopropyl alcohol = 4/1, elution rate =
As a result of analysis using 1.0 ml / min, detection wavelength = 254 nm), it was found that the optical purity of the obtained Michael adduct (30) was 44% ee.

Example 12 Preparation of BINOL Derivative 4

[0246]

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BINOL derivative 1 obtained in Example 1
240 mg (0.60 mmol) of (15) in THF
Dissolved in 5.0 ml, and cooled with ice, 23 mg of LiAlH ₄
(0.6 mmol) was added in four portions. After stirring at room temperature for 3 hours, Na ₂ SO ₄ .10H ₂ O was gradually added to the reaction solution. After the completion of hydrogen bubbling, 3 ml of 1N HCl was added, and the mixture was extracted three times with 20 ml of ethyl acetate. The ethyl acetate layer was collected, dried over anhydrous sodium sulfate, and concentrated. The concentrate was purified by flash column chromatography (ethyl acetate / n-hexane = 1/1) to obtain the target BINOL derivative 4 (31) in 208
mg. 98%).

¹ H-NMR (CDCl ₃ , δ ppm):
1.48-1.56 (m, 2H), 1.59-1.68 (m, 2H), 2.66 (t, J = 7.6Hz, 2
H), 3.52 (t, J = 6.2Hz, 2H), 5.0 (brs, 1H), 6.96-7.09 (m, 3H),
7.18-7.31 (m, 4H), 7.57 (s, 1H), 7.76-7.89 (m, 3H)

Example 13 Preparation of BINOL derivative 5

[0250]

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The BINOL derivative 4 obtained in Example 12
Dissolve 107.6 mg (0.3 mmol) of (31) in 5.0 ml of methylene chloride and, at 0 ° C., 81 μl (1.0 mmol) of acrylic acid chloride and triethylamine 2
00 μl (1.5 mmol) was added dropwise in order. 3 at 0 ° C
After stirring for 0 minutes, 4 ml of a saturated aqueous solution of ammonium chloride was added to the reaction solution, and the mixture was extracted three times with 5 ml of methylene chloride.
The methylene chloride layer was collected, dried over anhydrous sodium sulfate, and concentrated to obtain a divinyl ester as a main product (yield 49%).

The obtained divinyl ester was dissolved in 3 ml of methanol, and 100 mg of potassium carbonate was added thereto.
For 1 hour. 3 ml of a saturated aqueous solution of ammonium chloride was added to the reaction solution, and the mixture was extracted three times with 5 ml of ethyl acetate.
The ethyl acetate layer was collected, dried over anhydrous sodium sulfate, concentrated, and the concentrate was purified by flash column chromatography (ethyl acetate / n-hexane = 1/8) to obtain the BINOL derivative as the target substance. 5 (3
27.6 mg of 2) was obtained. Yield: 62% from divinyl ester.

¹ H-NMR (CDCl ₃ , δ ppm):
1.67-1.70 (m, 4H), 2.71 (t, J = 7.0Hz, 2H), 4.11 (t, J = 5.9Hz,
2H), 4.92 (s, 1H), 5.00 (s, 1H), 5.74 (dd, J = 1.4,10.4Hz, 1
H), 6.06 (dd, J = 10.4,17.3Hz, 1H), 6.31 (dd, J = 1.4,17.3Hz,
1H), 7.0-7.11 (m, 3H), 7.15-7.34 (m, 4H), 7.61 (s, 1H), 7.82
-7.93 (m, 3H)

Example 14 Production of {Si [(BINOL Derivative 5) ^2- ] ₂ }

[0255]

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The BINOL derivative 5 obtained in Example 13
(32) 49.4 mg (0.12 mmol) of THF
Dissolve in 2.0 ml and at 0 ° C., 8.6 μl of SiCl ₄
(0.06 mmol) was added dropwise. Next, 34 μl (0.24 mmol) of triethylamine was added dropwise, and the mixture was stirred at 0 ° C. for 1 hour to obtain the notation {Si [(BINOL)
Derivative 5) ^2- ] ₂ ｝ (33) in THF was prepared.

Example 15 Production of {Si [(BINOL derivative 6) ^2- ] ₂ }

[0258]

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The THF solution obtained in Example 14 was 2.0 m
2.0 g of PS-amine was added to
By stirring for a time, the indicated ｛Si [(BINOL
Derivatives 6) ² _2} The THF suspension was prepared (34).

{Si [(BINOL derivative 6) ^2- ] ₂ }
IR spectrum (nujol) of 1730 cm ^-1 (ester carbonyl)

Example 16 Preparation of BINOL Derivative 6

[0262]

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The ６３Si [(BINO) obtained in Example 15
L derivative 6) ^2- ] ₂ ] (34) To the THF suspension was added 2 ml of 1N HCl at 0 ° C. to cleave the metal-oxygen bond. The insoluble material was collected by filtration, and this was washed twice with 3 ml of water, TH
The resultant was washed twice with 3 ml of F and twice with 3 ml of diethyl ether, and dried under reduced pressure at room temperature for 3 hours to obtain 2.0 g of a target BINOL derivative 6 (35). Yield: ca. 87% (The yield was calculated based on the amount of the recovered BINOL derivative (15).)

IR spectrum (nujol) of BINOL derivative 6 (35): 3300 cm ^-1 (OH of phenol)

[0265] Production Example 17 {AlLi [(BINOL derivative 6) ^2- _2}

[0266]

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The BINOL derivative 6 obtained in Example 16
(35) 2.0 g (ca. 0.052 mmol / g) was suspended in 3.0 ml of anhydrous THF, and AlMe ₃ 3 was added at 0 ° C.
9 μl (1.02 M, 0.04 mmol) and n-B
26 μl of an n-hexane solution of uLi (1.53 M, 0.
04 mmol) in order to obtain the notation ｛[Al
TH of Li [(BINOL derivative 6) ^2- ] ₂ ｝ (36)
An F suspension was prepared.

Example 18 Catalytic Asymmetric Michael Addition Reaction

[0269]

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The ｛AlLi [(BI) obtained in Example 17
To a suspension of NOL derivative 6) ^2- ] ₂ } (36) in THF (ca. 10 mol% based on the substrate) was added 100 μl of malonic acid dibenzyl ester (38) at room temperature.
(0.4 mmol) and cyclohexenone (37) 3
9 μl (0.4 mmol) was added, and the mixture was stirred at room temperature for 72 hours. Thereafter, 2 ml of 1N HCl was added, the solid layer was collected by filtration, and the solid layer was washed three times with 10 ml of ethyl acetate. The ethyl acetate solution was collected, combined with the filtrate, dried over anhydrous sodium sulfate, and then purified by flash column chromatography (acetone / hexane = 1/9) to obtain 118.7 mg of Michael adduct (39). Yield: 78%

A column for optical resolution (Daicel Co., Ltd., trade name: CHIRAPAKAD, eluent: hexane / isopropyl alcohol = 4/1, elution rate =
As a result of analysis using 1.0 ml / min, detection wavelength = 254 nm), it was found that the optical purity of the obtained Michael adduct (39) was 56% ee.

[0272]

As described above, the present invention provides the first
Another object of the present invention is to provide a metal complex having a novel BINOL derivative as a ligand. The metal complex is useful as a catalyst for various asymmetric reactions such as an asymmetric nitroaldol reaction, an asymmetric aldol reaction, and an asymmetric Michael reaction.

The present invention also provides, secondly, a polymer metal complex having a novel polymer BINOL derivative useful as an asymmetric reaction catalyst as a ligand. The metal complex is easily separated from the reaction system after the asymmetric reaction, and the polymer B
The INOL ligand can be used repeatedly, so that the production process can be simplified and the production cost of the optically active compound can be reduced.

Further, according to the method for producing a polymer metal complex of the present invention, a polymer BINO having a three-dimensional structure such that a central metal can coordinate to a plurality of polymer BINOL ligands.
An L ligand can be formed, and a metal complex having the BINOL ligand can be efficiently produced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C07C 39/14 C07C 39/14 4H050 43/178 43/178 4J100 47/27 47/27 49/245 49 / 245 67/347 67/347 69/18 69/18 69/616 69/616 69/716 69/716 Z 201/12 201/12 205/15 205/15 205/16 205/16 205/26 205/26 235/66 235/66 C07F 1/02 C07F 1/02 1/04 1/04 1/06 1/06 3/06 3/06 5/00 5/00 D G 5/06 5/06 F 7/02 7/02 D 7/04 7/04 A 7/30 7/30 C 15/02 15/02 15/06 15/06 19/00 19/00 C08F 8/32 C08F 8/32 8/42 8/42 F-term (Reference) 4G069 AA06 BA27A BA27B BA28A BA28B BC01A BC04B BC15A BC16B BC41A BC42B BC49A BD03A BD03B BD05A BD05B BE05A BE06B BE08B BE19A BE19B BE32A BE37A BE37B BE43A BE45A BE47A02 AC81 A59 ACA ACB BA11 BA4 3 BA46 BJ50 BN10 BN30 BT12 BU22 FC54 FE13 4H039 CA60 CA66 CA72 CF10 CJ20 4H048 AA01 AA02 AB81 AC93 BB11 BB17 BB20 BB22 BB25 VA20 VA50 VA66 VA70 VA80 VB10 4H049 VN01 VP01 VQA4BA37H40 BA33A37A BB00H BB01H BC49H CA01 CA31 HA27 HA55 HA61 HA62 HB14 HB16 HB43 HC43 JA15

Claims (15)

[Claims] 1. A following general formula (1) ## STR1 ## _{[Ma (Mb) x (L} 1 2-) y] (1) { wherein, Ma, Mb represents a metal atom independently, x represents 0, 1, 2, or 3, y represents 2 or 3, and L ₁ represents the following general formula (2): [Wherein, R represents COR ¹ (r ¹ represents a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _1-6 alkoxy group or a group represented by Nr ² r ³ ; r ² and r ³ each independently represent a hydrogen atom or a C _1-6 alkyl group.) or Or ⁴ (r ⁴ is a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl). group, a COr ^5, r
⁵ is a C _1-6 alkyl group, C _2-6 alkenyl group, C _1-6
Represents an alkoxy group. R ¹ , R ² and R ³ each independently represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, a C _1-6 alkyl group,
Represents a C _2-6 alkenyl group, a C _1-6 alkoxy group, a phenyl group which may have a substituent or a tri-C _1-6 alkylsilylethynyl group, and n represents an integer of 1 to 8. ] A metal complex represented by｝. 2. The metal complex according to claim 1, wherein Ma is a Group III metal, a Group IV metal or a lanthanoid of the short-periodic table, and Mb is an alkali metal. 3. A following general formula (3) ## STR3 ## _{[Mc (Md) v (L} 2 2-) w] (3) { wherein, Mc, Md are each independently a metal atom, v represents 0, 1, 2 or 3, w represents 2 or 3, L ₂ represents the following general formula (4): [In the formula, (Poly) represents a polymer group having an amino group in the molecule, A represents a group represented by CO or —CH ₂ CH ₂ C (＝ O) O—, and n represents R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, a C _1-6 alkyl group,
Represents a C _2-6 alkenyl group, a C _1-6 alkoxy group, a phenyl group which may have a substituent or a tri-C _1-6 alkylsilylethynyl group. ].金属 The metal complex represented. 4. The metal complex according to claim 3, wherein said Mc is a Group III metal, a Group IV metal or a lanthanoid of the short periodic table, and said Md is an alkali metal. 5. The (Poly) is represented by the following formula (5). The metal complex according to claim 3, wherein the metal complex is a polystyrene derivative having a partial structure represented by the formula (where a represents an arbitrary natural number). 6. The metal complex according to claim 3, wherein (Poly) is a dendrimer having an amino group in the molecule. (A) The following general formula (1 '): [Ma' (Mb ')_x'(L₁'^2-)_y'] (1') ｛wherein, Ma 'represents a first metal, Mb' represents a second metal, x 'represents 0, 1, 2, or 3, and y' is 2 or 3 L₁'Is the following formula (2')[Wherein R ′ is COr¹'(R¹'Is a hydrogen atom, C_1-6
Alkyl group, C_2-6Alkenyl group or C_1-6Alkoxy
Represents a group. ) Or Or^Four'(R^Four'Is C_1-6Alkene
Group or COr^Five'(R^Five'Is C_1-6Alkyl group, C_2-6
Alkenyl group, C _1-6Represents an alkoxy group. ))
Then R¹', R^Two', R^Three'Are each independently a hydrogen atom,
Ano group, nitro group, halogen atom, C_1-6Alkyl group,
C_2-6Alkenyl group, C_1-6Has alkoxy group and substituent
Optionally substituted phenyl or tri-C_1-6Alkyl sil
Represents a ruethynyl group, and n ′ represents an integer of 1 to 8. ] Metal complex represented by｝
And (b) represented by the general formula (1 ′).
And a metal complex represented by the general formula (6):[Wherein (Poly) represents the same meaning as described above. 〕so
Reacting a polymer with an amino group in the molecule represented
[Ma '(Mb') having the general formula (3 ')_x'(L_Two'^2-)_y'] (3') where Ma ', Mb', x ', and y' have the same meanings as above.
Represents the taste, L_Two'Is the following formula (4')[Wherein (Poly) represents the same meaning as described above;^Four', R^Five', R⁶', Are each independently a hydrogen atom,
Cyano group, nitro group, halogen atom, C_1-6Alkyl
Group, C_2-6Alkenyl group, C_1-6Alkoxy group, substituent
A phenyl group or a tri-C_1-6Alkyl
Represents a silylethynyl group, n ′ represents an integer of 1 to 8, A ′ represents CO or —CH_TwoCH_TwoRepresented by C (= O) O-
Represents a group. ] A method for producing a metal complex represented by｝. 8. The system according to claim 7, wherein said Ma ′ is the third period of the short period periodic table.
The method for producing a metal complex according to claim 7, wherein the metal complex is a Group IV metal or a Group IV metal, and Mb 'is an alkali metal. 9. After the step (b), (c) removing a metal from the metal complex represented by the general formula (3 ′) to obtain a compound represented by the general formula (4 ′) , 1'-Bee
A step of obtaining a 2-naphthol derivative, and (d) adding a compound of a third metal and a compound of a fourth metal to the 1,1′-bi-2-naphthol derivative represented by the general formula (4 ′). General formula (3 ″): [Mc ′ (Md ′) _{v ′} (L ₂ ′ ²⁻ ) _{w ′} ] (3 ″) wherein L ₂ ′ is , Has the same meaning as above, and Mc ′ is the third
Md ′ represents a fourth metal, and v ′ represents
Represents 0, 1, 2, or 3, and w ′ represents 2 or 3. )
A method for producing a metal complex represented by the formula: 10. The method according to claim 1, wherein said Mc ′ is the second period of the short period periodic table.
A Group I metal, a Group IV metal or a lanthanoid;
The method for producing a metal complex according to claim 9, wherein is an alkali metal. 11. A compound of the general formula (4) (Wherein, R ⁴ , R ⁵ , R ⁶ , n, A and (Poly)
Represents the same meaning as described above. 1,1′-bi-2-naphthol derivative represented by the formula: The (Poly) is represented by the following formula (5): The 1,1′-bi-2-naphthol derivative according to claim 11, which is a polystyrene derivative having a partial structure represented by the following formula (where a represents an arbitrary natural number). 13. The 1,1′-bi-2-naphthol derivative according to claim 11, wherein (Poly) is a dendrimer having an amino group in the molecule. 14. The following general formula (3): [Mc (Md)_v(L_Two ^2-)_W] (3) (where Mc, Md, L_Two, V and w have the same meaning as above.
Represents taste. ) In the presence of the metal complex represented by the general formula
(7) R⁷CHO (7) (wherein, R⁷Is a linear or branched C_1-20Alkyl
Group, linear or branched C _1-20Alkenyl group, straight chain or
C_1-20Alkynyl group, C_3-8Cycloalkyl
Group, a phenyl group which may have a substituent or a substituent
Represents an aralkyl group which may be possessed. A)
A aldehyde compound and a compound represented by the general formula (8):⁸CH_TwoNO_Two(8) (where R⁸Is a hydrogen atom, a linear or branched C_1-20
Represents an alkyl group or a methylol group. Nit represented by)
General formula characterized by reacting with roalkane
(9)(Where R⁷, R⁸Represents the same meaning as described above, and C^*Is not
Represents a uniform carbon atom. ) Optically active nitroalco
Manufacturing method of the tool. 15. The following general formula (3): [Mc (Md)_v(L_Two)_W] (3) (where Mc, Md, L_Two, V and w have the same meaning as above.
Represents taste. ) In the presence of the metal complex represented by the general formula
(10)(Where R⁹, R^TenAre each independently linear or
Is the branch C_1-20Represents an alkyl group. Also, R⁹And R^TenWhen
Are bonded to form a carbon chain having 5 to 8 members.
Good. ), An α, β-unsaturated ketone represented by the general formula
(11) CHR¹¹(COR¹²) (COR¹³(11) (wherein, R¹¹Is a hydrogen atom or a linear or branched C
_1-20Represents an alkyl group; ¹², R¹³Are independent
And a hydrogen atom, a linear or branched C_1-20Alkyl group,
C which may have a substituent_7-20Aralkyl group, straight chain
Or branch C_1-20Having an alkoxy group or a substituent
Represents an optionally substituted phenyl group. )
General formula (12) characterized by the following:(Where R⁹, R^Ten, R¹¹, R¹², R¹³Is the same as above
Represents the taste, C^*Represents an asymmetric carbon atom. )
Manufacturing method of compound.