Organic compounds -- part of the class 532-570 series – Organic compounds – Sulfonic acids or salts thereof
Reexamination Certificate
2000-06-01
2001-12-04
Killos, Paul J. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Sulfonic acids or salts thereof
C562S030000, C562S109000, C568S881000
Reexamination Certificate
active
06326512
ABSTRACT:
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 11-343921, filed Dec. 2, 1999, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to an asymmetric producing method, and particularly a method of producing an optically active &bgr;-hydroxy sulfonic acid compound by catalytic asymmetric hydrogenation.
&bgr;-Hydroxy sulfonic acid compounds are among the important substances widely utilized in chemical industry and life science fields. For example, they are utilized as lubricants in electroplating of copper and Sn—Zn alloys and electrolytic pigmentation coating of aluminum, as stabilizers of disperse dyes, and as surface active ingredients of household cleansers. They also have high utility value as acid catalysts. Further, they attract attention in development of medicines based upon enzyme antagonism, since the sulfonyl group with a tetrahedrally arranged sp
3
sulfur atom antagonizes with carboxyl groups. Development of practical method of providing optically active compounds is required, since difference in chirality changes molecular assembly forms and greatly influence interface and bulk properties or characteristics and extent of biological activities.
Previously, reactions of epoxides or 1-chloro-2-alkanols with sodium sulfite and reduction of &bgr;-keto sulfonic acid compounds with metal hydrides have been reported as a method of producing a &bgr;-hydroxy sulfonic acid compound.
However, these previous methods described above can not form an optically active &bgr;-hydroxy sulfonic acid compound.
BRIEF SUMMARY OF THE INVENTION
The purpose of the present invention is to provide a method that can effectively produce an optically active &bgr;-hydroxy sulfonic acid compound in good asymmetric yield and chemical yield through simple operations.
The present inventors found that a kind of Ruthenium catalyst asymmetrically converts a &bgr;-keto sulfonic acid compound to an optically active &bgr;-hydroxy sulfonic acid compound in hydrogenation, as a result of repetition of wholehearted research paying attention to hydrogenation for solving the problem mentioned above, and completed the present invention.
Thus, the present invention provides a method of producing an optically active &bgr;-hydroxy sulfonic acid compound comprising hydrogenating a &bgr;-keto sulfonic acid compound represented by formula 1:
where R
1
represents an alkyl or a phenyl group, which may be substituted, and R
2
represents sodium or an alkyl, in an acidic solvent, in the presence of an asymmetric catalyst comprising a complex of bivalent Ru, having 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl as a ligand, to produce a compound represented by formula 2:
where R
1
and R
2
are as defined above, and * indicates an asymmetric carbon.
In the present invention, the Ru complex comprises [RuCl
2
((R) or (S)-binap)], [RuCl(C
6
H
6
)((R) or (S)-binap)]Cl, or [Ru(CH
3
COO)
2
((R) or (S)-binap)], where binap represents 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl.
Further, in the present invention, the acidic solvent is preferably acidified with hydrochloric acid, and has a hydrochloric acid concentration in the range of 5 to 25 mmol/L.
Further, in the present invention, the solvent preferably comprises methanol, ethanol, or acetone.
According to the present invention, an optically active &bgr;-hydrox ysulfonic acid compound can be effectively produced by asymmetric hydrogenation under atmospheric pressure.
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
REFERENCES:
patent: 5066815 (1991-11-01), Sayo et al.
patent: 5508435 (1996-04-01), Armstrong et al.
patent: 5532402 (1996-07-01), Noyori et al.
M. Kitamura, et al., 75th Symposium on Organic Synthesis, Japan, 5 pages, Jun. 2, 1999.
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M. Kitamura, et al., Enantiomer, vol. 1, pp. 281-303, “Synthesis of &agr;-Amino Phosphonic Acids by Asymmetric Hydrogenation”, 1996.
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M. Kitamura, et al., American Chemical Society, vol. 117, No. 10, pp. 2931-2932, “Asymmetric Hydrogenation of &bgr;-Keto Phosphonates: A Practical Way to Fosfomycin”, 1995.
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M. Kitamura, et al., Journal of the American Chemical Society, vol. 110, No. 2, pp. 629-631, “Homogeneous Asymmetric Hydrogenation of Functionalized Ketones”, 1988.
R. Noyori, et al., Journal of the American Chemical Society, vol. 109, No. 19, pp. 5856-5858, “Asymmetric Hydrogenation of &bgr;-Keto Carboxylic Esters. A Practical, Purely Chemical Access to &bgr;-Hydroxy Esters in High Enantiomeric Purity”, 1987.
Kanda Naoki
Kitamura Masato
Noyori Ryoji
Yoshimura Masahiro
Chaudhry Mahreen
Killos Paul J.
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
President of Nagoya University
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