Preparation of both enantiomers of malic and citramalic acid and other hydroxysuccinic acid derivatives by stereospecific hydrations of cis or trans 2-butene-1,4-dioic acids with resting cells of Clostridium formicoaceticum
✍ Scribed by Richard Eck; Helmut Simon
- Book ID
- 104203453
- Publisher
- Elsevier Science
- Year
- 1994
- Tongue
- French
- Weight
- 966 KB
- Volume
- 50
- Category
- Article
- ISSN
- 0040-4020
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✦ Synopsis
R)-Malic , Q-m&c, (R)-citramalic, (S)-citramalic, (2R,3S)-2-hydroxy-3-mctbylsuccinic and (2R,3S')-2,3dimctbyl-2-bydroxy&~inic acid were prepared on scales up to 25 mm01 by stermspccitic addition of water to different I-butenrA4dioic acid dcrivative.s catalyzed by resting cells af Chtridium formiwaceticum (Scheme 1). The (3R)-moncdcuterio (R)-and Qmalic acid as well as (R)-and (Sp&amak acid were prepared using frezzedricd cells in ?H20bulk The stereochemical purity oftbc products was in most casts > 99 %. @)-and (A')-malic acid (29 and la) are important compounds of the ' chid pool 'la. However, 2a is about thirty times more expensive than the Q-enantiomer. Only a few recent examples of their application in the synthesis of chiral products such as camitine lb, butenolidesle, 3,5-dihydroxy-6-oxohexanoatesld, 1,2-or 1,3-diols*e and oxiracetamlf shall be mentioned. For other uses of these synthons in organic synthesis see l.c. lagh. Further chiral synthons from 2-butene-1,4-dioic acids useful as synthons are the enantiomers of citramalic acid (2-hydroxy-2-metbylsuccinic acid), 2,3-dimethyl-2-hydroxysuccinic acid and 2-hydroxy-3methylsuccinic acid. (R)-Citramalic acid (4a) and the Q-enantiomer (3a) are synthons for phero-mone&b. (2R,35')-2,3-Dimethyl-2-hydroxysuccinic acid (Sa) has been used for the synthesis of the alkaloid jacobiie, whereas (2R,3S)-2-hydroxy-3-methylsuccinic acid (4b) is a synthon for 2-methyl-3hydroxy-butyrolactone@. For additional examples, in which 3a, 4a or 4b were used as synthons see l.c.24e. Many chemical, microbiological or enzymatic methods are known for the preparation of the aforementioned productsl~~&42493a-i. We describe the simple preparation of both enantiomers of malic and citramalic acid as well as the (2R,35')-enantiomers of 2-hydroxy-3-methyl-and 2,3-diiethyl-2-hydroxysuccinic acid with resting cells of Clostridhtm formicoaceticum (Scheme 1). Closthdia are used for the industrial synthesis of butanol, acetone, acetic acid and butyric acid&b. On a laboratory scale they are useful for many chiral carboxylates and chiral secondary alcohols'% In the preceding paper C. formicoaceticum grown on fructose and t%rmarate was used for the stereospecific reduction of 2-substituted fumarates and diiethyl 2-methyl-