JPH0957110A - Lewis acid catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a Lewis acid catalyst accelerated in reaction speed in org. synthesizing reaction due to various electron withdrawing reactions and in creased in catalytic activity by using a complex having a perfluoroalkanesulfonylamide group as a catalyst. SOLUTION: As a Lewis acid catalyst utilized in the production of medicines or agricultural chemicals, a substance represented by formula [X is -N(Tf <1> ) Tf <2> Tf <1> is -SO2 Rf <1> and Tf <2> is -SORf <2> (Rf <1> and R<2> are a lower perfluoroalkyl group}, R<1> is a cyclopentadienyl group, -OR<3> or -N(Tf <3> )R<4> , R<2> is a cylopenradienyl group,-OR<5> or-N(Tf <4> )R<6> Tf <3> is -SO2 Rf <3> , Tf <4> is -SO2 Rf <4> (Rf <4> Rf 4u$4x are a lower perfluoroalkyl group and R<3> -R<6> are a lower alkyl group, M is an element elected from rare earth elements and transition metals, n is an integer of the valency of M-2,-N(Tf <1> )Tf <2> , -N(Tf <3> )R<4> or -N(Tf <4> )R<6> is provided].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a general formula [I] useful for the production of pharmaceuticals, agricultural chemicals, various functional materials, and the intermediates thereof.

[0002]

[Chemical 33]

[Where X is -N (T_f ¹) T_f ²[T_f ¹Is-
SO₂R_f ¹Represents T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²
Are each independently a fluorine atom or a lower perfluoro group.
Represents a rukyl group. ). ], And R¹Is a replacement
Or an unsubstituted cyclopentadienyl group, -OR^ThreeOr
-N (T_f ^Three) R^FourRepresents R²Is a substituted or non-substituted
Clopentadienyl group, -OR^FiveOr -N (T_f ^Four) R⁶
[T_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^Three
And R_f ^FourAre each independently a fluorine atom or a lower
Represents a fluoroalkyl group. ), R^Three, R^Four, R^Five
And R⁶Each independently represent a lower alkyl group,
Or R^ThreeAnd R^Five, R^ThreeAnd R⁶, R ^FourAnd R^Five,
Alternatively, R^FourAnd R⁶Together with divalent groups
Form. ], M is an alkaline earth metal, rare earth element
Element, transition metal, boron, aluminum, gallium, in
Dium, thallium, silicon, germanium, tin, lead,
From arsenic, antimony, bismuth, selenium or tellurium
Represents the selected element, n is the valence of the corresponding M -2
Represents the number, -N (T_f ¹) T_f ², -N (T_f ^Three) R^FourOr
-N (T_f ^Four) R⁶At least one of ]
Lewis acid catalysts.

[0004]

Conventionally, when a metal salt is used as a Lewis acid catalyst in an organic synthesis reaction, ordinary metal salts such as halides, acetates and carbonates have extremely high solubility in a non-polar solvent such as dichloromethane. Since it is small, it is necessary to use an aprotic polar solvent such as ether or acetonitrile, which has a large coordination ability for metal ions. However, in these polar solvents, solvent molecules are strongly coordinated with the metal ion, so that there is a problem that the electrophilic Lewis acid catalytic activity of the metal ion with respect to the reaction substrate is extremely reduced.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a Lewis acid catalyst having an increased catalytic activity in an organic synthetic reaction by an electrophilic reaction.

In view of the above-mentioned conventional problems, the present inventors have earnestly studied, and as a result, by using a complex having various perfluoroalkanesulfonylimide groups as a catalyst, organic synthesis by various electrophilic reactions is performed. The reaction rate is accelerated in the reaction, the selectivity and the yield are improved, and by using an asymmetric ligand, an asymmetric compound can be produced with extremely high selectivity in an asymmetric synthesis reaction. And has reached the present invention.

That is, the first aspect of the present invention is the general formula [I]

[0008]

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[Wherein X is -N (T_f ¹) T_f ²[T_f ¹Is-
SO₂R_f ¹Represents T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²
Are each independently a fluorine atom or a lower perfluoro group.
Represents a rukyl group. ). ], And R¹Is a replacement
Or an unsubstituted cyclopentadienyl group, -OR^ThreeOr
-N (T_f ^Three) R^FourRepresents R²Is a substituted or non-substituted
Clopentadienyl group, -OR^FiveOr -N (T_f ^Four) R⁶
[T_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^Three
And R_f ^FourAre each independently a fluorine atom or a lower
Represents a fluoroalkyl group. ), R^Three, R^Four, R^Five
And R⁶Each independently represent a lower alkyl group,
Or R^ThreeAnd R^Five, R^ThreeAnd R⁶, R ^FourAnd R^Five,
Alternatively, R^FourAnd R⁶Together with divalent groups
Form. ], M is an alkaline earth metal, rare earth element
Element, transition metal, boron, aluminum, gallium, in
Dium, thallium, silicon, germanium, tin, lead,
From arsenic, antimony, bismuth, selenium or tellurium
Represents the selected element, n is the valence of the corresponding M -2
Represents the number, -N (T_f ¹) T_f ², -N (T_f ^Three) R^FourOr
-N (T_f ^Four) R⁶At least one of ]
It is a Lewis acid catalyst.

The second aspect of the present invention is the general formula [II]

[0011]

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[Wherein X'is a halogen atom, -OR
⁷(R⁷Represents a hydrogen atom or a lower alkyl group. ),-
OOCR⁸(R⁸Represents a lower alkyl group. ) Or -O
_ThreeSR⁹(R ⁹Is a lower alkyl group or substituted or non-substituted
Represents an alternative aryl group. ), R¹Is replaced or
Unsubstituted cyclopentadienyl group, -OR^ThreeOr -N
(T_f ^Three) R^FourRepresents R²Is a substituted or unsubstituted cyclo
Pentadienyl group, -OR^FiveOr -N (T_f ^Four) R⁶[T
_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^ThreeAnd
And R_f ^FourAre independently fluorine atom or lower perfume
Represents an oroalkyl group. ), R^Three, R^Four, R^FiveAnd
And R⁶Each independently represent a lower alkyl group, or
Is R^ThreeAnd R^Five, R^ThreeAnd R⁶, R^FourAnd R^Five,is there
Well, R^FourAnd R⁶Together form a divalent group
I do. ], M is an alkaline earth metal, a rare earth element,
Transition metals, boron, aluminum, gallium, indium
Aluminum, thallium, silicon, germanium, tin, lead,
Select from elemental, antimony, bismuth, selenium or tellurium
Represents the element to be exposed, and n is the integer of the corresponding M valence-2.
Represents ] The compound and general formula [III]

[0013]

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[Wherein X is -N (T _f ¹ ) T _f ² [T _f ¹ is-
Represents SO ₂ R _f ¹ , and T _f ² is —SO ₂ R _f ² (R _f ¹ and R _f ²
Each independently represents a fluorine atom or a lower perfluoroalkyl group. ) Represents. ], M'is -H,-
Represents Ag, an alkali metal or an alkaline earth metal, and y
Is 1 when M'is -H, -Ag or an alkali metal.
And is 2 when M ′ is an alkaline earth metal. ] The compound of general formula [I] characterized by reacting with a compound represented by

[0015]

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[Where X is -N (T_f ¹) T_f ²[T_f ¹Is-
SO₂R_f ¹Represents T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²
Are each independently a fluorine atom or a lower perfluoro group.
Represents a rukyl group. ). ], And R¹Is a replacement
Or an unsubstituted cyclopentadienyl group, -OR^ThreeOr
-N (T_f ^Three) R^FourRepresents R²Is a substituted or non-substituted
Clopentadienyl group, -OR^FiveOr -N (T_f ^Four) R⁶
[T_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^Three
And R_f ^FourAre each independently a fluorine atom or a lower
Represents a fluoroalkyl group. ), R^Three, R^Four, R^Five
And R⁶Each independently represent a lower alkyl group,
Or R^ThreeAnd R^Five, R^ThreeAnd R⁶, R ^FourAnd R^Five,
Alternatively, R^FourAnd R⁶Together with divalent groups
Form. ], M is an alkaline earth metal, rare earth element
Element, transition metal, boron, aluminum, gallium, in
Dium, thallium, silicon, germanium, tin, lead,
From arsenic, antimony, bismuth, selenium or tellurium
Represents the selected element, n is the valence of the corresponding M -2
Represents the number, -N (T_f ¹) T_f ², -N (T_f ^Three) R^FourOr
-N (T_f ^Four) R⁶At least one of ]
It is a method for producing a Lewis acid catalyst.

The third aspect of the present invention is to formula [IV]

[0018]

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[Wherein R ¹ represents a substituted or unsubstituted cyclopentadienyl group, -OR ³ or -N (T _f ³ ) R ⁴ and R ² represents a substituted or unsubstituted cyclopentadienyl group. , -OR ⁵ or -N (T _f ⁴ ) R ⁶ [T _f ³ is -SO ₂
Represents R _f ³ , T _f ⁴ represents —SO ₂ R _f ⁴ (R _f ³ and R _f ⁴ independently represent a fluorine atom or a lower perfluoroalkyl group), and R ³ , R ⁴ , and R ⁵ and R ⁶ each independently represent a lower alkyl group, or R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , or R ⁴ and R ⁶ together form a divalent group. Form a group. ]] Is represented. ] The compound and general formula [V]

[0020]

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[Where X is -N (T _f ¹ ) T _f ² [T _f ¹ is-
Represents SO ₂ R _f ¹ , and T _f ² is —SO ₂ R _f ² (R _f ¹ and R _f ²
Each independently represents a fluorine atom or a lower perfluoroalkyl group. ) Represents. ], M represents an element selected from alkaline earth metals, rare earth elements, transition metals, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, selenium or tellurium. , M represents an integer corresponding to the valence of M. ] The compound of general formula [I] characterized by reacting with a compound represented by

[0022]

[Chemical 40]

[Wherein X is -N (T_f ¹) T_f ²[T_f ¹Is-
SO₂R_f ¹Represents T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²
Are each independently a fluorine atom or a lower perfluoro group.
Represents a rukyl group. ). ], And R¹Is a replacement
Or an unsubstituted cyclopentadienyl group, -OR^ThreeOr
-N (T_f ^Three) R^FourRepresents R²Is a substituted or non-substituted
Clopentadienyl group, -OR^FiveOr -N (T_f ^Four) R⁶
[T_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^Three
And R_f ^FourAre each independently a fluorine atom or a lower
Represents a fluoroalkyl group. ), R^Three, R^Four, R^Five
And R⁶Each independently represent a lower alkyl group,
Or R^ThreeAnd R^Five, R^ThreeAnd R⁶, R ^FourAnd R^Five,
Alternatively, R^FourAnd R⁶Together with divalent groups
Form. ], M is an alkaline earth metal, rare earth element
Element, transition metal, boron, aluminum, gallium, in
Dium, thallium, silicon, germanium, tin, lead,
From arsenic, antimony, bismuth, selenium or tellurium
Represents the selected element, n is the valence of the corresponding M -2
Represents the number, -N (T_f ¹) T_f ², -N (T_f ^Three) R^FourOr
-N (T_f ^Four) R⁶At least one of ]
It is a method for producing a Lewis acid catalyst.

Furthermore, the fourth aspect of the present invention is to formula [II]

[0025]

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[Wherein X'is a halogen atom, -OR
⁷(R⁷Represents a hydrogen atom or a lower alkyl group. ),-
OOCR⁸(R⁸Represents a lower alkyl group. ) Or -O
_ThreeSR⁹(R ⁹Is a lower alkyl group or substituted or non-substituted
Represents an alternative aryl group. ), R¹Is replaced or
Unsubstituted cyclopentadienyl group, -OR^ThreeOr -N
(T_f ^Three) R^FourRepresents R²Is a substituted or unsubstituted cyclo
Pentadienyl group, -OR^FiveOr -N (T_f ^Four) R⁶[T
_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^ThreeAnd
And R_f ^FourAre independently fluorine atom or lower perfume
Represents an oroalkyl group. ), R^Three, R^Four, R^FiveAnd
And R⁶Each independently represent a lower alkyl group, or
Is R^ThreeAnd R^Five, R^ThreeAnd R⁶, R^FourAnd R^Five,is there
Well, R^FourAnd R⁶Together form a divalent group
I do. ], M is an alkaline earth metal, a rare earth element,
Transition metals, boron, aluminum, gallium, indium
Aluminum, thallium, silicon, germanium, tin, lead,
Select from elemental, antimony, bismuth, selenium or tellurium
Represents the element to be exposed, and n is the integer of the corresponding M valence-2.
Represents ] The compound and general formula [III]

[0027]

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[Where X is -N (T _f ¹ ) T _f ² [T _f ¹ is-
Represents SO ₂ R _f ¹ , and T _f ² is —SO ₂ R _f ² (R _f ¹ and R _f ²
Each independently represents a fluorine atom or a lower perfluoroalkyl group. ) Represents. ], M'is -H,-
Represents Ag, an alkali metal or an alkaline earth metal, and y
Is 1 when M'is -H, -Ag or an alkali metal.
And is 2 when M ′ is an alkaline earth metal. ] It is a Lewis acid catalyst obtained by making it react with the compound shown by these.

Furthermore, the fifth aspect of the present invention is to provide a compound represented by the general formula [I
V]

[0030]

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[Wherein R ¹ represents a substituted or unsubstituted cyclopentadienyl group, -OR ³ or -N (T _f ³ ) R ⁴ and R ² represents a substituted or unsubstituted cyclopentadienyl group. , -OR ⁵ or -N (T _f ⁴ ) R ⁶ [T _f ³ is -SO ₂
Represents R _f ³ , T _f ⁴ represents —SO ₂ R _f ⁴ (R _f ³ and R _f ⁴ independently represent a fluorine atom or a lower perfluoroalkyl group), and R ³ , R ⁴ , and R ⁵ and R ⁶ each independently represent a lower alkyl group, or R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , or R ⁴ and R ⁶ together form a divalent group. Form a group. ]] Is represented. ] The compound and general formula [V]

[0032]

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[Where X is -N (T _f ¹ ) T _f ² [T _f ¹ is-
Represents SO ₂ R _f ¹ , and T _f ² is —SO ₂ R _f ² (R _f ¹ and R _f ²
Each independently represents a fluorine atom or a lower perfluoroalkyl group. ) Represents. ], M represents an element selected from alkaline earth metals, rare earth elements, transition metals, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, selenium or tellurium. , M represents an integer corresponding to the valence of M. ] It is a Lewis acid catalyst obtained by making it react with the compound shown by these.

The present invention will be described in detail below. As M, which is the central element of the Lewis acid catalyst represented by the general formula [I] of the present invention, not only titanium, aluminum, boron, etc., which have been widely used as Lewis acids, but also many other elements can be used. It can be used, specifically, alkaline earth metals, rare earth elements, transition metals, boron, aluminum, gallium, indium, thallium,
Silicon, germanium, tin, lead, arsenic, antimony,
An element selected from bismuth, selenium or tellurium can be used.

The above-mentioned alkaline earth metal in the present invention means beryllium, magnesium, calcium, strontium, barium or radium. Also,
The rare earth element in the present invention is scandium,
Indicates yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium. Further, the above transition metal in the present invention, titanium, zirconium, hafnium, vanadium,
Indicates niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium or mercury.

The compound represented by the general formula [I] of the present invention is
It is used as a ligand for M, which is the central element of the isosic acid catalyst.
What is X is -N (T_f ¹) T_f ²[T_f ¹Is -SO₂
R_f ¹Represents T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²Haso
Each independently a fluorine atom or lower perfluoroalkyl
Represents a hydroxyl group. ). ] Is used and R¹As
A substituted or unsubstituted cyclopentadienyl group, -OR^Three
Or -N (T_f ^Three) R^FourIs used and R²As a replacement
Or unsubstituted cyclopentadienyl group, -OR^FiveAlso
Is -N (T_f ^Four) R⁶[T_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs
-SO₂R_f ^Four(R _f ^ThreeAnd R_f ^FourAre each independently fluorine
Represents an atom or a lower perfluoroalkyl group. )
Then R^Three, R^Four, R^FiveAnd R⁶Are independently lower al
Represents a kill group, or R^ThreeAnd R^Five, R^Threeand
R⁶, R^FourAnd R^FiveOr R^FourAnd R⁶But
To form a divalent group. ] Is used. this
These ligands X and R¹And R²What a combination
Or a compound represented by the general formula [I] of the present invention.
In order for a substance to exhibit sufficient Lewis acid activity,
Attracting perfluoroalkanesulfonylimide group-
N (T_f ¹) T_f ², -N (T_f ^Three) R^FourOr -N (T_f ^Four)
R⁶Need to have at least one of
In order to exhibit stronger Lewis acid activity, these
-Has more fluoroalkanesulfonylimide groups
Preferably.

The above-mentioned lower alkyl group in the present invention means an alkyl group having a straight or branched chain having 1 to 10 carbon atoms, and specifically, for example, methyl group, ethyl group, n-propyl group. Group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, ter
t-butyl group, n-pentyl group, n-hexyl group, n-
Examples thereof include a heptyl group and an n-octyl group. Further, the above-mentioned lower perfluoroalkyl group in the present invention refers to a perfluoroalkyl group having a linear or branched chain having 1 to 10 carbon atoms, and specifically, for example, trifluoromethyl group, pentafluoroethyl group. Base,
n-heptafluoropropyl group, iso-heptafluoropropyl group, n-nonafluorobutyl group, iso-nonafluorobutyl group, sec-nonafluorobutyl group,
tert-nonafluorobutyl group, n-undecafluoropentyl group, n-tridecafluorohexyl group, n-
Examples thereof include a pentadecafluoroheptyl group and an n-heptadecafluorooctyl group.

Further, the above R ³ , R ⁴ and R in the present invention are
⁵ and R ⁶ are each independently a lower alkyl group, or R ³ contained in R ¹ or R ⁵ contained in R ⁴ and R ^2.
Or two of R ⁶ are in a set, that is, R ³
And R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , or
R ⁴ and R ⁶ may together form a divalent group, for example:

[0039]

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[0040]

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[0041]

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[0042]

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And the like. All of these exemplified divalent groups are asymmetric groups, and when having such asymmetric divalent group, the Lewis acid catalyst represented by the general formula [I] of the present invention is , Especially important.

That is, in such a case, the compound represented by the general formula [I] of the present invention becomes a catalyst having both Lewis acidity and an asymmetric ligand, and this catalyst is used in the organic synthesis reaction. In that case, the Lewis acidity accelerates the reaction rate to improve the selectivity and yield, and at the same time,
Due to the action of the asymmetric ligand, an asymmetric compound can be produced with extremely high selectivity. Therefore, especially when it has such an asymmetric ligand, the Lewis acid catalyst represented by the general formula [I] of the present invention can be used in various fields such as pharmaceuticals, agricultural chemicals and liquid crystal materials. Is a very useful catalyst.

The Lewis acid catalyst represented by the above general formula [I] of the present invention can be used in any reaction as long as it is an organic synthesis reaction by an electrophilic reaction.
Diels-Alder reaction, hetero-Diels-Alder reaction, Michael addition reaction, Friedel-Crafts reaction, acylation reaction of alcohols and amines, ene reaction, allylation reaction of aldehydes, conjugated addition reaction of amines, glycosyl The reaction is a polymerization reaction of olefins and the like. In these reactions, it is a very useful and extremely excellent catalyst as described above.

The Lewis acid catalyst represented by the general formula [I] of the present invention as described above can be produced by various methods. For example, the general formula [II]

[0047]

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[Wherein X'is a halogen atom, -OR
⁷(R⁷Represents a hydrogen atom or a lower alkyl group. ),-
OOCR⁸(R⁸Represents a lower alkyl group. ) Or -O
_ThreeSR⁹(R ⁹Is a lower alkyl group or substituted or non-substituted
Represents an alternative aryl group. ), R¹Is replaced or
Unsubstituted cyclopentadienyl group, -OR^ThreeOr -N
(T_f ^Three) R^FourRepresents R²Is a substituted or unsubstituted cyclo
Pentadienyl group, -OR^FiveOr -N (T_f ^Four) R⁶[T
_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^ThreeAnd
And R_f ^FourAre independently fluorine atom or lower perfume
Represents an oroalkyl group. ), R^Three, R^Four, R^FiveAnd
And R⁶Each independently represent a lower alkyl group, or
Is R^ThreeAnd R^Five, R^ThreeAnd R⁶, R^FourAnd R^Five,is there
Well, R^FourAnd R⁶Together form a divalent group
I do. ], M is an alkaline earth metal, a rare earth element,
Transition metals, boron, aluminum, gallium, indium
Aluminum, thallium, silicon, germanium, tin, lead,
Select from elemental, antimony, bismuth, selenium or tellurium
Represents the element to be exposed, and n is the integer of the corresponding M valence-2.
Represents ] The compound and general formula [III]

[0049]

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[Wherein, X is -N (T _f ¹ ) T _f ² [T _f ¹ is-
Represents SO ₂ R _f ¹ , and T _f ² is —SO ₂ R _f ² (R _f ¹ and R _f ²
Each independently represents a fluorine atom or a lower perfluoroalkyl group. ) Represents. ], M'is -H,-
Represents Ag, an alkali metal or an alkaline earth metal, and y
Is 1 when M'is -H, -Ag or an alkali metal.
And is 2 when M ′ is an alkaline earth metal. ] It can manufacture by reacting with the compound shown by these.

The Lewis acid catalyst represented by the general formula [I] of the present invention has the general formula [IV]

[0052]

[Chemical 51]

[Wherein R ¹ represents a substituted or unsubstituted cyclopentadienyl group, -OR ³ or -N (T _f ³ ) R ⁴ and R ² represents a substituted or unsubstituted cyclopentadienyl group. , -OR ⁵ or -N (T _f ⁴ ) R ⁶ [T _f ³ is -SO ₂
Represents R _f ³ , T _f ⁴ represents —SO ₂ R _f ⁴ (R _f ³ and R _f ⁴ independently represent a fluorine atom or a lower perfluoroalkyl group), and R ³ , R ⁴ , and R ⁵ and R ⁶ each independently represent a lower alkyl group, or R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , or R ⁴ and R ⁶ together form a divalent group. Form a group. ]] Is represented. ] The compound and general formula [V]

[0054]

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[Wherein X is -N (T _f ¹ ) T _f ² [T _f ¹ is-
Represents SO ₂ R _f ¹ , and T _f ² is —SO ₂ R _f ² (R _f ¹ and R _f ²
Each independently represents a fluorine atom or a lower perfluoroalkyl group. ) Represents. ], M represents an element selected from alkaline earth metals, rare earth elements, transition metals, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, selenium or tellurium. , M represents an integer corresponding to the valence of M. ] It can manufacture also by making it react with the compound shown by these.

The compound represented by the general formula [II] or the general formula [I] which is the starting material in these production methods of the present invention
The compound represented by II], the compound represented by the general formula [IV] and the compound represented by the general formula [V] are commercially available or can be easily produced by a known method. Can also be easily obtained.

The reaction in these production methods of the present invention is usually carried out using a solvent, but the solvent used is not particularly limited, and commonly used ones may be widely used. Yes, for example, water, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-
Alcohols such as butanol, tert-butanol, n-pentyl alcohol and n-hexyl alcohol,
Aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, benzene, toluene, o-xylene, m
-Aromatic hydrocarbons such as xylene and p-xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane (EDC), chlorobenzene, o-dichlorobenzene, m-dichlorobenzene and p-dichlorobenzene , Ethers such as diethyl ether, dioxane, tetrahydrofuran (THF) and ethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate and γ-butyrolactone, acetonitrile, benzonitrile etc. Nitriles, tertiary amines such as pyridine, N, N-
Acid amides such as dimethylformamide (DMF), N, N-dimethylacetamide (DMAc) and N-methylpyrrolidone, sulfur-containing compounds such as dimethyl sulfoxide (DMSO) and sulfolane, nitro compounds such as nitromethane and nitroethane, acetic acid Examples thereof include organic acids such as propionic acid, butyric acid, and isobutyric acid, and organic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and isobutyric anhydride.

[0058]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0059]

Example 1 (Preparation of catalyst) Bistrifluoromethanesulfonylimidic acid (562 m
g, 2 mmol) was dissolved in dichloromethane (8 mL), and the compound of the formula [VI] (295 μL,
1 mmol) was added at room temperature under an argon atmosphere. After stirring at room temperature, the solvent was distilled off under reduced pressure. The solid residue was washed with pentane and recrystallized from pentane / ether to give the compound of formula [VII].

[0060]

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[0061]

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Example 2 (Preparation of catalyst) The compound (5 mmol) represented by the formula [VIII] was dissolved in anhydrous acetonitrile, and a solution of bistrifluoromethanesulfonylimide silver (10 mmol) in anhydrous acetonitrile was added and stirred. . After filtration, a hexane layer was carefully formed on the colorless filtrate. After standing for 24 hours, the compound of the formula [IX] was obtained as white crystals.

[0063]

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[0064]

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Example 3 (Preparation of catalyst) A compound (5 mmol) represented by the formula [X] was dissolved in anhydrous acetonitrile, and a solution of bistrifluoromethanesulfonylimide silver (10 mmol) in anhydrous acetonitrile was added and stirred. . After filtration, a hexane layer was carefully formed on the colorless filtrate. After leaving for 24 hours, the formula [X
I] was obtained as a crystal.

[0066]

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[0067]

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Example 4 (Preparation of catalyst ) Bistrifilamide of (1R, 2R) -1,2-diphenylethylenediamine represented by the formula [XII] (48)
mg, 0.1 mmol) in tetrahydrofuran (2 m
L) was reacted with sodium hydride (0.2 mmol) at room temperature for 30 minutes. Bistrifluoromethanesulfonylimide ytterbium (101 mg, 0.1 m
mol) and water (1.2 mmol) were added and stirred. After stirring for 1 hour, the solvent was distilled off under reduced pressure to obtain the compound of the formula [XII
I] was obtained.

[0069]

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[0070]

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Example 5 (Preparation of catalyst) A compound represented by the formula [XIV] was obtained in exactly the same manner as in Example 4 except that yttrium bistrifluoromethanesulfonylimide was used instead of ytterbium. .

[0072]

[Chemical formula 61]

Example 6 (Friedel-Crafts reaction) The compound represented by the formula [VII] (0.07 mmol) obtained in Example 1 was dissolved in nitroethane (3 mL), and anisole (109 μL, 1 mmol) was dissolved therein. And acetic anhydride (188 μL, 2 mmol) was added at room temperature. After stirring at room temperature for 5 minutes, it was diluted with ether (5 mL) and saturated NaHCO ₃ aqueous solution (10 mL) was added.
After filtration, the filtrate was extracted with ether three times (15 mL in total). The organic layers were combined and washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. Purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1), and purified by the formula [X
Compounds represented by V] a (R = -CH ₃₎ was obtained in 86% yield.

[0074]

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Example 7 (Friedel-Crafts reaction) The compound of the formula [VII] (0.02 mmol) obtained in Example 1 was dissolved in nitroethane (3 mL), and diphenyl ether (1 mmol) and anhydrous were added thereto. Acetic acid (188 μL, 2 mmol) was added at room temperature.
After stirring at room temperature for 1 hour, the mixture was diluted with ether (5 mL), and saturated aqueous NaHCO ₃ solution (10 mL) was added. After filtration, the filtrate was extracted with ether three times (15 mL in total). The organic layers were combined and washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. Purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1), and purified by the formula [X
Compounds represented by V] a (R = -C ₅ H ₆₎ was obtained in 60% yield.

Example 8 (Acylation reaction of alcohols) The compound (0.01 mmol) represented by the formula [VII] obtained in Example 1 was dissolved in dichloromethane (3 mL), and 1-phenyl-1 was added thereto. -Propanol (137
μL, 1 mmol) and acetic anhydride (113 μL, 1.
2 mmol) was added at room temperature. After stirring at room temperature for 1 minute, it was diluted with ether (5 mL) and saturated aqueous NaHCO ₃ solution (10 mL) was added. After filtration, the filtrate was extracted with ether three times (15 mL in total). The organic layers were combined and washed with saturated saline. After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 1-acetoxy-1-phenylpropane in a yield of 90%.

Example 9 (Acylation reaction of alcohols) The compound (0.02 mmol) represented by the formula [VII] obtained in Example 1 was dissolved in dichloromethane (3 mL), and phenol (1 mmol) and Acetic anhydride (113 μL, 1.2 mmol) was added at room temperature. After stirring at room temperature for 1 minute, dilute with ether (5 mL),
Saturated aqueous NaHCO ₃ solution (10 mL) was added. After filtration, the filtrate was extracted with ether three times (15 mL in total).
The organic layers were combined and washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to quantitatively obtain acetoxybenzene.

Example 10 (Acylation reaction of alcohols)
(V) Acetoxybenzene was quantitatively obtained in the same manner as in Example 9 except that toluene was used as the solvent instead of dichloromethane.

Example 11 (Acylation reaction of alcohols)
The compound of formula [VII] (0.02 mmol) obtained in Example 1 was dissolved in dichloromethane (3 mL), and 2,6-bis (tert-butyl) -4- was added thereto.
Methylphenol (1 mmol) and acetic anhydride (11
3 μL, 1.2 mmol) was added at room temperature. 1 at room temperature
After stirring for an hour, dilute with ether (5 mL) and sat.
Aqueous aHCO ₃ solution (10 mL) was added. After filtration, the filtrate was extracted with ether three times (15 mL in total). The organic layers were combined and washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to quantitatively obtain 1-acetoxy-2,6-bis (tert-butyl) -4-methylbenzene.

Example 12 (Acylation reaction of alcohols)
Using acetonitrile instead of dichloromethane as response) solvent, except that the stirring time 1 hour was set to 1 minute in the same manner as in Example 11 1-acetoxy-2,6-bis (ter
tert-Butyl) -4-methylbenzene was quantitatively obtained.

Example 13 (Acylation reaction of amines) The compound of the formula [VII] (0.006 mmol) obtained in Example 1 was dissolved in dichloromethane (3 mL), and 1-phenylethylamine ( 1 mmo
1) and acetic anhydride (113 μL, 1.2 mmol) were added at 0 ° C. After stirring at 0 ° C. for 5 minutes, dilute with ethyl acetate (5 mL) and add saturated aqueous NaHCO ₃ solution (10 m
L) was added. After filtration, the filtrate was extracted with ethyl acetate three times (15 mL in total). The organic layers were combined and washed with saturated saline. After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to quantitatively obtain N- (1-phenylethyl) acetamide.

Example 14 (Acylation reaction of amines) The compound (0.01 mmol) represented by the formula [VII] obtained in Example 1 was dissolved in dichloromethane (3 mL), and 1-phenylethylamine ( 1 mmol)
And benzoic anhydride (1.2 mmol) were added at 0 ° C. After stirring for 15 minutes at 0 ° C., ethyl acetate (5 mL)
Diluted with and saturated aqueous NaHCO ₃ solution (10 mL) was added. After filtration, the filtrate was thrice with ethyl acetate (15 mL in total).
Extracted. The organic layers were combined and washed with saturated saline. After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to quantitatively obtain N- (1-phenylethyl) benzamide.

Example 15 (Conjugate addition reaction of amines) The compound (0.02 mmol) represented by the formula [VII] obtained in Example 1 was converted into tetrahydrofuran (2 mL).
And the compound of the formula [XVI] (1 m
mol) and phenylmethylamine (155 μL,
1.5 mmol) was added at room temperature. After stirring, it was diluted with ethyl acetate (5 mL) and saturated aqueous NaHCO ₃ solution (10
mL) was added. After filtration, the filtrate was extracted with ethyl acetate three times (15 mL in total). The organic layers were combined and washed with saturated saline. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give the compound represented by the formula [XVII] in a yield of 25%.

[0084]

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[0085]

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Example 16 (Diels-Alder reaction) The compound (0.01 mmol) represented by the formula [VII] obtained in Example 1 was dissolved in dichloromethane (2 mL), and methacrolein (166 μL, 2 mmo) was dissolved therein.
1) and 1-acetoxy-1,3-butadiene (16
9 μL, 1 mmol) was added at 0 ° C. After stirring for 3 hours at 0 ° C., dilute with ether (5 mL) and sat.
It was added CO ₃ solution (10 mL). After filtration, the filtrate was extracted with ether three times (15 mL in total). The organic layers were combined and washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1) gave 6-formyl-6-methylcyclohex-2-enyl acetate in a yield of 54%.

Example 17 (Hetero-Diels-Arda
Over reaction) the compound represented by the formula [XIII] obtained in Example 4 (0.1 mmol) was dissolved in toluene (3 mL), -
Cool to 78 ° C. and add to it butyl glyoxylate (13
0 mg, 1 mmol) and 3- (tert-butyldimethylsilyloxy) -1-methoxy-1,3-butadiene (257 mg, 1.2 mmol) were added. -7
After stirring at 8 ° C for 30 minutes, it was diluted with ether (15 mL) and filtered. The filtrate was cooled to 0 ° C., trifluoroacetic acid (0.08 mL, 1.05 mmol) was added, and saturated N 2
aHCO ₃ aqueous solution was added, and 3 times with ether (total 15 m
L) extracted. The organic layers were combined and washed with saturated saline. After drying the organic layer with anhydrous magnesium sulfate, under reduced pressure,
The solvent was distilled off. Purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 2/1), butyl (S) -2,3-dihydro-4-oxo-4
H-pyran-2-carboxylate was obtained with a yield of 69% and an optical purity of 70% ee.

Example 18 (Hetero-Diels-Arda
-Reaction) In the same manner as in Example 17, except that the compound represented by the formula [XIV] obtained in Example 5 was used instead of the compound represented by the formula [XIII] obtained in Example 4, (S) -2,3-dihydro-4-oxo-4H-pyran-2-carboxylate yield 59%, optical purity 43%
Obtained in ee.

Example 19 (Hetero-Diels-Arda
-Reaction) Bistrifilamide of (1R, 2R) -1,2-diphenylethylenediamine (48 ) represented by the formula [XII]
mg, 0.1 mmol) in tetrahydrofuran (2 m
L), and added thereto bistrifluoromethanesulfonylimide ytterbium (101 mg, 0.1 mmo
1) and water (1.2 mmol) were added and stirred.
After stirring for 1 hour, the solvent was distilled off under reduced pressure. Toluene (3
mL) and cooled to −78 ° C., to which butyl glyoxylate (130 mg, 1 mmol) and 3-
(Tert-Butyldimethylsilyloxy) -1-methoxy-1,3-butadiene (257 mg, 1.2 mmo
l) was added. After stirring at −78 ° C. for 30 minutes, it was diluted with ether (15 mL) and filtered. The filtrate was cooled to 0 ° C. and trifluoroacetic acid (0.08 mL, 1.05 mm
ol), a saturated aqueous NaHCO ₃ solution was added, and the mixture was extracted with ether three times (15 mL in total). Combine the organic layers,
Washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. Silica gel column chromatography (eluent: hexane / ethyl acetate =
2/1) to obtain butyl (S) -2,3-dihydro-4-oxo-4H-pyran-2-carboxylate with a yield of 55% and an optical purity of 65% ee.

Example 20 (Hetero-Diels-Arda
Over reaction) was used bistrifluoromethanesulfonylimide yttrium (0.1 mmol) in place of bis-trifluoromethanesulfonyl imide ytterbium Example 1
Butyl (S) -2,3-dihydro-in exactly the same manner as in 9.
4-oxo-4H-pyran-2-carboxylate was obtained with a yield of 36% and an optical purity of 64% ee.

[0091]

By using the Lewis acid catalyst of the present invention, the reaction rate in the organic synthesis reaction by the electrophilic reaction is accelerated, and the selectivity and the yield are improved. Especially,
By using an asymmetric ligand, an asymmetric compound can be produced with extremely high selectivity in an asymmetric synthesis reaction.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junmichi Maruta 2805 Imafuku Nakadai, Kawagoe City, Saitama Central Chemical Co., Ltd. (72) Inventor Hiroaki Sakaguchi 5253 Oki Ube, Ube City, Yamaguchi Prefecture Central Glass Chemical Laboratory Co., Ltd.

Claims (43)

[Claims] 1. A compound represented by the general formula [I]:[In the formula, X is -N (T_f ¹) T_f ²[T_f ¹Is -SO₂R_f ¹To
Represent, T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²Are each
Independently a fluorine atom or a lower perfluoroalkyl group
Represent. ). ], And R¹Is substituted or unsubstituted
Cyclopentadienyl group, -OR^ThreeOr -N
(T_f ^Three) R^FourRepresents R²Is a substituted or unsubstituted cyclo
Pentadienyl group, -OR^FiveOr -N (T_f ^Four) R⁶[T
_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^ThreeAnd
And R_f ^FourAre independently fluorine atom or lower perfume
Represents an oroalkyl group. ), R^Three, R^Four, R^FiveAnd
And R⁶Each independently represent a lower alkyl group, or
Is R^ThreeAnd R^Five, R^ThreeAnd R⁶, R ^FourAnd R^Five,is there
Well, R^FourAnd R⁶Together form a divalent group
I do. ], M is an alkaline earth metal, a rare earth element,
Transition metals, boron, aluminum, gallium, indium
Aluminum, thallium, silicon, germanium, tin, lead,
Select from elemental, antimony, bismuth, selenium or tellurium
Represents the element to be exposed, and n is the integer of the corresponding M valence-2.
, -N (T_f ¹) T_f ², -N (T_f ^Three) R^FourOr-
N (T_f ^Four) R⁶At least one of ]
Lewis acid catalyst. 2. R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , or R ⁴ and R ⁶ are taken together. Embedded image Embedded image Embedded image The Lewis acid catalyst according to claim 1, which forms a group represented by: 3. R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , or R ⁴ and R ⁶ together. The Lewis acid catalyst according to claim 1, which forms a group represented by: 4. The Lewis acid catalyst according to claim 1, wherein R ¹ and R ² are cyclopentadienyl groups. 5. R ¹ is —OR ³ and R ² is —OR ⁵ (R ³
And R ⁵ each independently represent a lower alkyl group. )
The Lewis acid catalyst according to claim 1, wherein 6. The Lewis acid catalyst according to claim ^{5, wherein} R ³ and R ⁵ are iso-propyl groups. 7. R ¹ is —OR ³ and R ² is —OR ⁵ (R ³
And R ⁵ together form a divalent group. )
The Lewis acid catalyst according to claim 1, wherein 8. R ³ and R ⁵ are joined together The Lewis acid catalyst according to claim 7, which forms a group represented by: 9. R ¹ is --N (T _f ³ ) R ⁴ and R ² is --N.
(T _f ⁴⁾ R ⁶ [T _f ³ represents ^{_{-SO 2 R f 3, T f}} 4 is -SO
₂ R _f ⁴ (R _f ³ and R _f ⁴ each independently represent a fluorine atom or a lower perfluoroalkyl group), and R
⁴ and R ⁶ together form a divalent group. ]
The Lewis acid catalyst according to claim 1, wherein 10. R ⁴ and R ⁶ are taken together and embedded image The Lewis acid catalyst according to claim 9, which forms a group represented by: 11. T _f ¹ , T _f ² , T _f ³ and T _f ⁴ are --SO _2.
The Lewis acid catalyst according to claim 1, which is CF ₃ . 12. The Lewis acid catalyst according to claim 1, wherein M is an element selected from rare earth elements, titanium, zirconium, hafnium, boron or aluminum. 13. The Lewis acid catalyst according to claim 1, wherein M is an element selected from yttrium, ytterbium, titanium or zirconium. 14. A compound represented by the general formula [II]:[In the formula, X'is a halogen atom, -OR⁷(R⁷Is a hydrogen atom
Alternatively, it represents a lower alkyl group. ), -OOCR⁸(R⁸Is
Represents a lower alkyl group. ) Or -O_ThreeSR⁹(R ⁹Is low
A primary alkyl group or a substituted or unsubstituted aryl group
Represent. ), R¹Is a substituted or unsubstituted cyclope
Interdienyl group, -OR^ThreeOr -N (T_f ^Three) R^FourThe table
Then R²Is a substituted or unsubstituted cyclopentadienyl
Group, -OR^FiveOr -N (T_f ^Four) R⁶[T_f ^ThreeIs -SO₂R_f
^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^ThreeAnd R_f ^FourEach
Independently fluorine atom or lower perfluoroalkyl group
Represents ), R^Three, R^Four, R^FiveAnd R⁶Are each
Independently represents a lower alkyl group, or R^Threeand
R^Five, R^ThreeAnd R⁶, R^FourAnd R^FiveOr R^FourAnd
And R⁶Together form a divalent group. ] To the table
M is an alkaline earth metal, a rare earth element, a transition metal,
Arsenic, aluminum, gallium, indium, tariu
Aluminum, silicon, germanium, tin, lead, arsenic, antimony
Element selected from nitrogen, bismuth, selenium or tellurium
Where n represents the integer of the corresponding M valence-2. ]so
A compound of the formula [III][In the formula, X is -N (T_f ¹) T_f ²[T_f ¹Is -SO₂R_f ¹To
Represent, T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²Are each
Independently a fluorine atom or a lower perfluoroalkyl group
Represent. ). ], M'is -H, -Ag, al
Represents a potassium metal or an alkaline earth metal, and y is M'-
1 in the case of H, -Ag or alkali metal,
It is 2 when M'is an alkaline earth metal. ]
General formula characterized by reacting with a compound
[I][In the formula, X is -N (T_f ¹) T_f ²[T_f ¹Is -SO₂R_f ¹To
Represent, T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²Are each
Independently a fluorine atom or a lower perfluoroalkyl group
Represent. ). ], And R¹Is substituted or unsubstituted
Cyclopentadienyl group, -OR^ThreeOr -N
(T_f ^Three) R^FourRepresents R²Is a substituted or unsubstituted cyclo
Pentadienyl group, -OR^FiveOr -N (T_f ^Four) R⁶[T
_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^ThreeAnd
And R_f ^FourAre independently fluorine atom or lower perfume
Represents an oroalkyl group. ), R^Three, R^Four, R^FiveAnd
And R⁶Each independently represent a lower alkyl group, or
Is R^ThreeAnd R^Five, R^ThreeAnd R⁶, R ^FourAnd R^Five,is there
Well, R^FourAnd R⁶Together form a divalent group
I do. ], M is an alkaline earth metal, a rare earth element,
Transition metals, boron, aluminum, gallium, indium
Aluminum, thallium, silicon, germanium, tin, lead,
Select from elemental, antimony, bismuth, selenium or tellurium
Represents the element to be exposed, and n is the integer of the corresponding M valence-2.
, -N (T_f ¹) T_f ², -N (T_f ^Three) R^FourOr-
N (T_f ^Four) R⁶At least one of ]
Method for producing Lewis acid catalyst. 15. R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , or R ⁴ and R ⁶ are taken together. Embedded image Embedded image Embedded image 15. The method for producing a Lewis acid catalyst according to claim 14, which forms a group represented by: 16. R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , or R ⁴ and R ⁶ together. 15. The method for producing a Lewis acid catalyst according to claim 14, which forms a group represented by: 17. The method for producing a Lewis acid catalyst according to claim 14, wherein R ¹ and R ² are cyclopentadienyl groups. 18. R ¹ is —OR ³ and R ² is —OR ⁵ (R
³ and R ⁵ each independently represent a lower alkyl group. )
15. The method for producing a Lewis acid catalyst according to claim 14. 19. The method for producing a Lewis acid catalyst according to claim 18, wherein R ³ and R ⁵ are iso-propyl groups. 20. R ¹ is —OR ³ and R ² is —OR ⁵ (R
³ and R ⁵ together form a divalent group. )
15. The method for producing a Lewis acid catalyst according to claim 14. 21. R ³ and R ⁵ are joined together 21. The method for producing a Lewis acid catalyst according to claim 20, which forms a group represented by: 22. R ¹ is -N (T _f ³ ) R ⁴ and R ² is-.
N (T _f ⁴⁾ R ⁶ [T _f ³ represents ^{_{-SO 2 R f 3, T f}} 4 is -S
And O ₂ R _f ⁴ (R _f ³ and R _f ⁴ each independently represent a fluorine atom or a lower perfluoroalkyl group),
R ⁴ and R ⁶ together form a divalent group. ] The manufacturing method of the Lewis acid catalyst of Claim 14 which is these. 23. R ⁴ and R ⁶ are joined together 23. The method for producing a Lewis acid catalyst according to claim 22, wherein a group represented by: is formed. 24. T _f ¹ , T _f ² , T _f ³ and T _f ⁴ are --SO _2.
Manufacturing method of a Lewis acid catalyst according to any one of CF ₃ in which claims 14 to 23. 25. The method for producing a Lewis acid catalyst according to claim 14, wherein M is an element selected from rare earth elements, titanium, zirconium, hafnium, boron or aluminum. 26. The method for producing a Lewis acid catalyst according to claim 14, wherein M is an element selected from yttrium, ytterbium, titanium or zirconium. 27. X ′ is a halogen atom or —OR ⁷ (R ⁷
Represents a lower alkyl group. ) And M'is -H or -Ag. 27. The method for producing a Lewis acid catalyst according to claim 14. 28. The method according to claim 14, wherein X'is a chlorine atom or an iso-propyl group, and M'is -H or -Ag.
The method for producing a Lewis acid catalyst according to claim 26. 29. A compound represented by the general formula [IV]:[Wherein, R¹Is a substituted or unsubstituted cyclopentadiene
Nyl group, -OR^ThreeOr -N (T_f ^Three) R^FourRepresents R²Is
Substituted or unsubstituted cyclopentadienyl group, -OR
^FiveOr -N (T_f ^Four) R⁶[T_f ^ThreeIs -SO₂R_f ^ThreeRepresents
T_f ^FourIs -SO₂R_f ^Four(R_f ^ThreeAnd R_f ^FourAre independently
Represents a fluorine atom or a lower perfluoroalkyl group
You. ), R^Three, R^Four, R^FiveAnd R⁶Are independent
Represents a lower alkyl group, or R^ThreeAnd R^Five, R
^ThreeAnd R⁶, R^FourAnd R^FiveOr R^FourAnd R⁶But
Together they form a divalent group. ]] Is represented. ]so
The compounds shown and the general formula [V][In the formula, X is -N (T_f ¹) T_f ²[T_f ¹Is -SO₂R_f ¹To
Represent, T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²Are each
Independently a fluorine atom or a lower perfluoroalkyl group
Represent. ). ], M is an alkaline earth metal, rare
Earth elements, transition metals, boron, aluminum, galiu
Aluminum, indium, thallium, silicon, germanium, stainless steel
, Lead, arsenic, antimony, bismuth, selenium or te
Represents an element selected from Lulu, m is the valence of the corresponding M
Represents an integer. ] Reacting with a compound represented by
The general formula [I] is characterized by:[In the formula, X is -N (T_f ¹) T_f ²[T_f ¹Is -SO₂R_f ¹To
Represent, T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²Are each
Independently a fluorine atom or a lower perfluoroalkyl group
Represent. ). ], And R¹Is substituted or unsubstituted
Cyclopentadienyl group, -OR^ThreeOr -N
(T_f ^Three) R^FourRepresents R²Is a substituted or unsubstituted cyclo
Pentadienyl group, -OR^FiveOr -N (T_f ^Four) R⁶[T
_f ^ThreeIs -SO₂R_f ^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^ThreeAnd
And R_f ^FourAre independently fluorine atom or lower perfume
Represents an oroalkyl group. ), R^Three, R^Four, R^FiveAnd
And R⁶Each independently represent a lower alkyl group, or
Is R^ThreeAnd R^Five, R^ThreeAnd R⁶, R ^FourAnd R^Five,is there
Well, R^FourAnd R⁶Together form a divalent group
I do. ], M is an alkaline earth metal, a rare earth element,
Transition metals, boron, aluminum, gallium, indium
Aluminum, thallium, silicon, germanium, tin, lead,
Select from elemental, antimony, bismuth, selenium or tellurium
Represents the element to be exposed, and n is the integer of the corresponding M valence-2.
, -N (T_f ¹) T_f ², -N (T_f ^Three) R^FourOr-
N (T_f ^Four) R⁶At least one of ]
Method for producing Lewis acid catalyst. 30. R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , or R ⁴ and R ⁶ are taken together. Embedded image Embedded image Embedded image 30. The method for producing a Lewis acid catalyst according to claim 29, wherein the group represented by: is formed. 31. R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , or R ⁴ and R ⁶ are taken together. 30. The method for producing a Lewis acid catalyst according to claim 29, wherein the group represented by: is formed. 32. The method for producing a Lewis acid catalyst according to claim 29, wherein R ¹ and R ² are cyclopentadienyl groups. 33. R ¹ is -OR ³ and R ² is -OR ⁵ (R
³ and R ⁵ each independently represent a lower alkyl group. )
30. The method for producing a Lewis acid catalyst according to claim 29. 34. The process for producing a Lewis acid catalyst according to claim 33, wherein R ³ and R ⁵ are iso-propyl groups. 35. R ¹ is —OR ³ and R ² is —OR ⁵ (R
³ and R ⁵ together form a divalent group. )
30. The method for producing a Lewis acid catalyst according to claim 29. 36. R ³ and R ⁵ are joined together 36. The method for producing a Lewis acid catalyst according to claim 35, wherein the group represented by: is formed. 37. R ¹ is -N (T _f ³ ) R ⁴ and R ² is-.
N (T _f ⁴⁾ R ⁶ [T _f ³ represents ^{_{-SO 2 R f 3, T f}} 4 is -S
And O ₂ R _f ⁴ (R _f ³ and R _f ⁴ each independently represent a fluorine atom or a lower perfluoroalkyl group),
R ⁴ and R ⁶ together form a divalent group. ] The method for producing a Lewis acid catalyst according to claim 29. 38. R ⁴ and R ⁶ are joined together 38. The method for producing a Lewis acid catalyst according to claim 37, wherein the group represented by: is formed. 39. T _f ¹ , T _f ² , T _f ³ and T _f ⁴ are --SO _2.
The method for producing a Lewis acid catalyst according to any one of claims 29 to 38, which is CF ₃ . 40. The method for producing a Lewis acid catalyst according to claim 29, wherein M is an element selected from rare earth elements, titanium, zirconium, hafnium, boron or aluminum. 41. The method for producing a Lewis acid catalyst according to claim 29, wherein M is an element selected from yttrium, ytterbium, titanium or zirconium. 42. A compound represented by the general formula [II]:[In the formula, X'is a halogen atom, -OR⁷(R⁷Is a hydrogen atom
Alternatively, it represents a lower alkyl group. ), -OOCR⁸(R⁸Is
Represents a lower alkyl group. ) Or -O_ThreeSR⁹(R ⁹Is low
A primary alkyl group or a substituted or unsubstituted aryl group
Represent. ), R¹Is a substituted or unsubstituted cyclope
Interdienyl group, -OR^ThreeOr -N (T_f ^Three) R^FourThe table
Then R²Is a substituted or unsubstituted cyclopentadienyl
Group, -OR^FiveOr -N (T_f ^Four) R⁶[T_f ^ThreeIs -SO₂R_f
^ThreeRepresents T_f ^FourIs -SO₂R_f ^Four(R_f ^ThreeAnd R_f ^FourEach
Independently fluorine atom or lower perfluoroalkyl group
Represents ), R^Three, R^Four, R^FiveAnd R⁶Are each
Independently represents a lower alkyl group, or R^Threeand
R^Five, R^ThreeAnd R⁶, R^FourAnd R^FiveOr R^FourAnd
And R⁶Together form a divalent group. ] To the table
M is an alkaline earth metal, a rare earth element, a transition metal,
Arsenic, aluminum, gallium, indium, tariu
Aluminum, silicon, germanium, tin, lead, arsenic, antimony
Element selected from nitrogen, bismuth, selenium or tellurium
Where n represents the integer of the corresponding M valence-2. ]so
A compound of the formula [III][In the formula, X is -N (T_f ¹) T_f ²[T_f ¹Is -SO₂R_f ¹To
Represent, T_f ²Is -SO₂R_f ²(R_f ¹And R_f ²Are each
Independently a fluorine atom or a lower perfluoroalkyl group
Represent. ). ], M'is -H, -Ag, al
Represents a potassium metal or an alkaline earth metal, and y is M'-
1 in the case of H, -Ag or alkali metal,
It is 2 when M'is an alkaline earth metal. ]
Lewis acid obtained by reacting with a compound
catalyst. 43. A compound represented by the general formula [IV]: [In the formula, R ¹ represents a substituted or unsubstituted cyclopentadienyl group, —OR ³ or —N (T _f ³ ) R ⁴ , and R ² represents a substituted or unsubstituted cyclopentadienyl group, —OR
⁵ or -N (T _f ⁴⁾ R ⁶ [T _f ³ represents -SO ₂ R _f ^3,
T _f ⁴ represents a (. Which represents a fluorine atom or a lower perfluoroalkyl group in each R _f ³ and R _f ^{4 _{independently) -SO 2 R f 4, R}} 3, R 4, R 5 and R ⁶ each Independently represents a lower alkyl group, or R ³ and R ⁵ , R
³ and R ⁶ , R ⁴ and R ⁵ , or R ⁴ and R ⁶ together form a divalent group. ]] Is represented. ] And a compound of the general formula [V] [Wherein, X is -N (T _f ¹ ) T _f ² [T _f ¹ represents -SO ₂ R _f ¹ , T _f ² represents -SO ₂ R _f ² (R _f ¹ and R _f ² are respectively Independently represents a fluorine atom or a lower perfluoroalkyl group). ], M represents an element selected from alkaline earth metals, rare earth elements, transition metals, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, selenium or tellurium. , M represents an integer corresponding to the valence of M. ] The Lewis acid catalyst obtained by making it react with the compound shown by these.