Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2001-11-15
2002-08-27
Kifle, Bruck (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S125000, C564S168000
Reexamination Certificate
active
06441231
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel optically active quarternary ammonium salt having C
2
-symmetric axial chirality, a method for producing thereof, and an intermediate for producing the salt and a method for producing the intermediate. Further, the present invention relates to a method for producing optically active &agr;-amino acid derivatives by stereoselective alkylation using the salts as a phase-transfer catalyst.
2. Description of the Related Art
A method is reported that cincona alkaloid derivatives are used as a phase-transfer catalyst for producing optically active &agr;-amino acid derivatives expressed by a general formula (XXI):
wherein
R
5
is an alkyl group having 1 to 6 carbon atoms which may be branched or form a cyclic group; an allyl or substituted allyl group having 3 to 9 carbon atoms which may be branched or form a cyclic group; an aralkyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom, an aryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom, or a heteroaryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom; a heteroaralkyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom, an aryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom, or a heteroaryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom; or a propargyl or substituted propargyl group which having 3 to 9 carbon atoms which may be branched; and
* is a newly produced chiral center (Corey, E. J. et al. J. Am. Chem. Soc., 1997, 119, 12414).
The above-mentioned compound of general formula (XXI) are produced by stereoselectively alkylating a glycine derivative expressed by a general formula (XIX):
in the two phase system comprised or organic solvent and water, with a compound of general formula (XX):
R
5
—W (XX)
wherein
R
5
is an alkyl group having 1 to 6 carbon atoms which may be branched or form a cyclic group; an allyl or substituted allyl group having 3 to 9 carbon atoms which may be branched or form a cyclic group; an aralkyl group which may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom, an aryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom, or a heteroaryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom; a heteroaralkyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom, an aryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom, or a heteroaryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom; or a propargyl or substituted propargyl group which having 3 to 9 carbon atoms which may be branched; and W is a functional group having leaving ability.
However, in the above-mentioned conventional method, halogenized solvent should be used as a solvent and since reaction temperature should be very low for producing the chiral derivatives with high purity, above-mentioned method is not used for industrial production.
Furthermore, since the phase-transfer catalyst is prepared from cincona alkaloid, it is difficult to modify or prepare derivatives of a catalyst having an excellent stereoselectivity based on the above-mentioned phase-transfer catalyst.
On the other hand, it is not known that optically active quarternary ammonium salt with axial chirality is prepared and used for stereoselective alkylation as a phase-transfer catalyst.
SUMMARY OF THE INVENTION
The purpose of the present invention is to provide an optically active quarternary ammonium salt with axial chirality, particularly their spiro derivatives, as a phase-transfer catalyst. The quarternary ammonium salt of the present invention converts glycine derivatives into optically active &agr;-amino acid derivatives by stereoselectively alkylating the glycine derivatives. Moreover, the purpose of the present invention is to provide an intermediates useful for production of the novel quarternary ammonium salt.
The present invention provides a compound of general formula (I):
wherein
R
1
and R
2
are groups independently selected from the group consisting of a hydrogen atom; an alkyl group having 1 to 6 carbon atoms which may be branched or form a cyclic group; an alkenyl group having 2 to 6 carbon atoms which may be branched or form a cyclic group; an alkynyl group having 2 to 6 carbon atoms which may contain branched or cyclic structure; an aralkyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom; a heteroaralkyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom; an aryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom; a heteroaryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom; a (C
1
to C
3
alkoxy) carbonyl group; a carbamoyl group; a N-(C
1
to C
4
alkyl) carbamoyl group; and a N,N-di(C
1
to C
4
alkyl) carbamoyl group (wherein alkyl may be the same or different), and
R
1
and R
2
may be the same or different;
Ar
1
and Ar
2
are groups independently selected from the group consisting of an aryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom; and a heteroaryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halogen atom, and
Ar
1
and Ar
2
may be the same or different;
X
−
is a halide anion; and
Y and Z are groups independently selected from the group consisting of a hydrogen atom; a halogen atom; an alkyl group having 1 to 4 carbon atoms; and an alkoxy group having 1 to 3 carbon atoms, and Y and Z may be the same or different or may form a single bond. Thus, the above purpose are achieved.
In a preferred embodiment of the present invention, the above compound is a spiro type and Y and Z form a single bond, and the compound is expressed by a general formula (II):
In a preferred embodiment of the present invention, Ar
1
and Ar
2
are &bgr;-naphthyl groups, each Ar
1
and Ar
2
is bound to &agr;-site of the other group, X
−
is a bromide anion, and the compound is expressed by a general formula (III):
In a preferred embodiment of the present invention, both R
1
and R
2
are phenyl, or both R
1
and R
2
are &bgr;-naphthyl.
Moreover, the present invention provides a method for producing the compound of the general formula (I), comprising reacting a compound of general formula (IV):
wherein
R
1
and R
2
are groups independently selected from the group consisting of a hydrogen atom; an alkyl group having 1 to 6 carbon atoms which may be branched or form a cyclic group; an alkenyl group having 2 to 6 carbon atoms which may be branched or form a cyclic group; an alkynyl group having 2 to 6 carbon atoms which may contain branched or cyclic structure; an aralkyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon ato
Kifle Bruck
Nagase & Co. Ltd.
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