Stereochemistry of Krebs' Cycle Hydrations and Related Reactions

Oscar Gawron; Andrew J. Glaid; Thomas P. Fondy

doi:10.1021/ja01478a021

Stereochemistry of Krebs' Cycle Hydrations and Related Reactions

Oscar Gawron, Andrew J. Glaid, Thomas P. Fondy

Research output: Contribution to journal › Article › peer-review

44 Scopus citations

Abstract

3-Deuterio-l-malic acid obtained from the fumarase catalyzed hydration of fumaric acid in D₂O is shown to have the erythro configuration by n.m.r. comparison with stereospecifically synthesized threo-3-deuterio-dl-malic acid. The fumarase and aspartase systems thus operate by a trans mechanism as do the β-methylaspartase and cis-aconitase systems. Brewster's rules are applied to the problem of the stereochemistry of citric acid synthesized in the Krebs cycle and a configuration related to d-malic acid is arrived at. This configuration plus the 2 configuration of d-isocitric acid permits depiction of the stereochemical pathway of the cis-aconitase system and of the reactions of the Krebs cycle. The possibility that cis-aconitase exhibits a preferred direction for addition of OH, with concomitant trans addition of H, is discussed.

Original language	English (US)
Pages (from-to)	3634-3640
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	83
Issue number	17
DOIs	https://doi.org/10.1021/ja01478a021
State	Published - Sep 5 1961
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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abstract = "3-Deuterio-l-malic acid obtained from the fumarase catalyzed hydration of fumaric acid in D2O is shown to have the erythro configuration by n.m.r. comparison with stereospecifically synthesized threo-3-deuterio-dl-malic acid. The fumarase and aspartase systems thus operate by a trans mechanism as do the β-methylaspartase and cis-aconitase systems. Brewster's rules are applied to the problem of the stereochemistry of citric acid synthesized in the Krebs cycle and a configuration related to d-malic acid is arrived at. This configuration plus the 2 configuration of d-isocitric acid permits depiction of the stereochemical pathway of the cis-aconitase system and of the reactions of the Krebs cycle. The possibility that cis-aconitase exhibits a preferred direction for addition of OH, with concomitant trans addition of H, is discussed.",

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T1 - Stereochemistry of Krebs' Cycle Hydrations and Related Reactions

AU - Gawron, Oscar

AU - Glaid, Andrew J.

AU - Fondy, Thomas P.

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N2 - 3-Deuterio-l-malic acid obtained from the fumarase catalyzed hydration of fumaric acid in D2O is shown to have the erythro configuration by n.m.r. comparison with stereospecifically synthesized threo-3-deuterio-dl-malic acid. The fumarase and aspartase systems thus operate by a trans mechanism as do the β-methylaspartase and cis-aconitase systems. Brewster's rules are applied to the problem of the stereochemistry of citric acid synthesized in the Krebs cycle and a configuration related to d-malic acid is arrived at. This configuration plus the 2 configuration of d-isocitric acid permits depiction of the stereochemical pathway of the cis-aconitase system and of the reactions of the Krebs cycle. The possibility that cis-aconitase exhibits a preferred direction for addition of OH, with concomitant trans addition of H, is discussed.

AB - 3-Deuterio-l-malic acid obtained from the fumarase catalyzed hydration of fumaric acid in D2O is shown to have the erythro configuration by n.m.r. comparison with stereospecifically synthesized threo-3-deuterio-dl-malic acid. The fumarase and aspartase systems thus operate by a trans mechanism as do the β-methylaspartase and cis-aconitase systems. Brewster's rules are applied to the problem of the stereochemistry of citric acid synthesized in the Krebs cycle and a configuration related to d-malic acid is arrived at. This configuration plus the 2 configuration of d-isocitric acid permits depiction of the stereochemical pathway of the cis-aconitase system and of the reactions of the Krebs cycle. The possibility that cis-aconitase exhibits a preferred direction for addition of OH, with concomitant trans addition of H, is discussed.

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Stereochemistry of Krebs' Cycle Hydrations and Related Reactions

Abstract

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