158705-99-8Relevant academic research and scientific papers
Stereocontrolled Synthesis of (2R,3S)-2-Methylisocitrate, a Central Intermediate in the Methylcitrate Cycle
Darley, Dan J.,Selmer, Thorsten,Clegg, William,Harrington, Ross W.,Buckel, Wolfgang,Golding, Bernard T.
, p. 3991 - 3999 (2007/10/03)
2-Methylisocitrate (=3-hydroxybutane-1,2,3-tricarboxylic acid) is an intermediate in the oxidation of propanoate to pyruvate (=2-oxopropanoate) via the methylcitrate cycle in both bacteria and fungi (Scheme 1). Stereocontrolled syntheses of (2R,3S)- and (2S,3R)-2-methylisocitrate (98% e.e.) were achieved starting from (R)- and (S)-lactic acid (=(2R)- and (2S)-2-hydroxypropanoic acid), respectively. The dispiroketal (6S,7S,15R)-15-methyl-1,8,13,16-tetraoxadispiro[5.0.5.4]hexadecan-14-one (2a) derived from (R)-lactic acid was deprotonated with lithium diisopropylamide to give a carbanion that was condensed with diethyl fumarate (Scheme 3). The configuration of the adduct diethyl (2S)-2-[(6S,7S,14R)-14-methyl-15-oxo-1,8,13,16-tetraoxadispiro[5.0.5.4] hexadec-14-yl]butanedioate (3a) was assigned by consideration of possible transition states for the fumarate condensation (cf. Scheme 2), and this was confirmed by a crystal-structure analysis. The adduct was subjected to acid hydrolysis to afford the lactone 4a of (2R,3S)-2-methylisocitrate and hence (2R,3S)-2-methylisocitrate. Similarly, (S)-lactic acid led to (2S,3R)-2-methylisocitrate. Comparison of 2-methylisocitrate produced enzymatically with the synthetic enantiomers established that the biologically active isomer is (2R,3S)-2-methylisocitrate.
The Fungal Biosynthesos of 3-Nitropropionic Acid: Is the Decarboxylation of L-Nitrosuccinate an Enzymatic Reaction?
Baxter, Robert L.,Smith, Shona L.,Martin, Jennifer R.,Hanley, A. Bryan
, p. 2297 - 2300 (2007/10/02)
In vitro enzymatic hydrolysis of diethyl (RS)-nitrosuccinate 2c by pig liver esterase at pH 7.8 affords 3-nitropropionic acid 1 indicating that the decarboxylation of (RS)-nitrosuccinate 2b is spontaneous under physiological conditions.In the in vivo synthesis of 1 from L-aspartate by cells of Penicillium atrovenetum, which involves oxidation of L-aspartate to nitrosuccinic acid, the decarboxylation of the nitrosuccinate may not require a specific biological catalyst.
