Chemistry: molecular biology and microbiology – Micro-organism – tissue cell culture or enzyme using process...
Patent
1996-12-12
1998-06-30
Achutamurthy, Ponnathapura
Chemistry: molecular biology and microbiology
Micro-organism, tissue cell culture or enzyme using process...
435135, 435142, 560190, 560201, 562571, C12P 100, C12P 744, C07C 6934
Patent
active
057732400
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to a method for producing optically active .alpha.-substituted carboxylic acid derivatives and antipodes thereof which are useful as raw materials for various liquid crystals and as synthetic intermediates for various optically active medicines or agricultural chemicals.
BACKGROUND ART
Of optically active .alpha.-substituted carboxylic acid derivatives, a method for producing, for example, an optically active .alpha.-methylhexanoic acid ester has been reported in which .alpha.-methylhexanoic acid is esterified stereoselectively using lipase (E. K. Heinz, Tetrahedron: Asymmetry, 2(3), 165 (1991)). However, this method is not satisfactory in terms of both yield and optical purity when industrial production is intended.
Of optically active .alpha.-substituted carboxylic acid derivatives, an optically active .alpha.-methylsuccinic acid monoester might possibly be obtained by partially hydrolyzing an optically active .alpha.-methylsuccinic acid diester using an alkali catalyst or the like. In this case, however, the reaction products are obtained as a mixture of .alpha.-methylsuccinic acid, .alpha.-methylsuccinic acid-1-monoester, .alpha.-methylsuccinic acid-4-monoester and .alpha.-methylsuccinic acid diester. Thus, it is difficult to obtain the product of interest selectively and at high purity. Furthermore, when a racemic mixture is used as a substrate, an ability to perform optical resolution cannot be expected from such a mode of reaction.
On the other hand, as a method for selectively synthesizing an .alpha.-methylsuccinic acid monoester, the method as described below using itaconic anhydride as a starting material is known in general (Barnett, Morris, Biochem. J., 40, 451 (1946)). ##STR3##
However, the .alpha.-methylsuccinic acid monoester obtained by the above method is a racemate and an optically active compound cannot be obtained in such a mode of reaction.
There has also been reported a method in which itaconic acid or dimethyl itaconate is asymmetrically reduced to thereby obtain optically active .alpha.-methylsuccinic acid or optically active dimethyl .alpha.-methylsuccinate. However, since this method needs an expensive asymmetric catalyst, it cannot be regarded as an industrially advantageous method (T. Morimoto et al., Chem., Pharm. Bull., 41(6), 1149 (1993)).
On the other hand, a method has been reported in which an .alpha.-methylsuccinic acid diester is hydrolyzed by porcine pancreatic lipase to thereby obtain .alpha.-methylsuccinic acid-1-monoester (Eryka Guibe-Jampel et al., J. Chem. Soc., Chem. Commun., 1080, 1987).
Although the optical purity and position selectivity of the ester obtained by this method are fairly high, it cannot be regarded as an industrially advantageous method since an expensive, animal-derived enzyme is used. Further, Japanese Unexamined Patent Publication No. 2-195890 discloses a method in which an .alpha.-methylsuccinic acid diester is hydrolyzed by a microorganism-derived enzyme to thereby obtains .alpha.-methylsuccinic acid-4-monoester. In this method, position selectivity is high with the ratio of 4-monoester in the resultant products being 95 -98%. However, stereoselective hydrolysis is hardly achieved. When a racemic diester is used as a starting material, the optical purity of the resultant products is only 16% e.e.
As methods for producing, for example, optically active .beta.-hydroxyisobutyric acid derivatives out of optically active .alpha.-substituted carboxylic acid derivatives, there have been reported a method of asymmetric reduction of a .beta.-keto acid ester, a method of optical resolution, a method of oxidation of 1,3-diol, a method of .beta.-hydroxylation of fatty acid, a method of direct fermentation, and the like as a chemical method or a method using a microorganism. Of these method, a method of producing .beta.-hydroxyisobutyric acid using the metabolic pathway of a microorganism is practiced in an industrial scale (Japanese Examined Patent Publications No. 59-21599, No. 59-21600, No. 60-16235, No
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Ikemoto Tetsuya
Kobayashi Yoshimasa
Ozaki Eiji
Sakashita Keiichi
Sakimae Akihiro
Achutamurthy Ponnathapura
Mitsubishi Rayon Co. Ltd.
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