763-51-9Relevant articles and documents
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 (2003)
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.
Fungal Biosynthesis of 3-Nitropropanoic Acid
Baxter, Robert L.,Hanley, A. Bryan,Chan, Henry W.-S.,Greenwood, Suzanne L.,Abbot, Elaine M.,et al.
, p. 2495 - 2502 (2007/10/02)
The origin of 3-nitropropanoic acid 1 in the fungus Penicillium atrovenetum has been examined using a combination of stable isotope methods.The incorporation of 13C and 15N from DL-aspartic acid 2a, 18O from 18O2, 15N from DL-diethyl nitrosuccinate 6 and 2H from L-aspartate, DL-aspartate and from (2S,3R)-- and (2S,3S)--aspartates indicate a biosynthetic pathway L-aspartate 2 -> (S)-nitrosuccinate 5 -> 1.Mature cells of P. atrovenetum which produce 3-nitropropanoate dehydrogenase catalyse an apparent futile cycle between 1 and 3-nitroacrylate 3 with loss of the stereospecific integrity of the hydrogen at the 2-position of 1.
