151378-64-2Relevant academic research and scientific papers
Kinetics and Mechanism of syn-Elimination of Ammonia from (2S,3R)-3-Methylaspartic Acid by Methylaspartase
Archer, Catherine H.,Gani, David
, p. 140 - 142 (1993)
Methylaspartase catalyses the slow syn-elimination of ammonia from the (2S,3R)--diastereoisomer of the natural substrate (2S,3S)-3-methylaspartic acid, to give mesaconic acid; the reaction does not involve C-3 epimerisation followed by normal anti-elimination, ruling-out the possibility of a carbanion intermediate, but, displays large primary deuterium isotope effects consistent with concerted C-H and C-N bond cleavage.
Syntheses of (2S,3R)- and (2S,3R)2H>- 3-Methylaspartic acid: Slow Substrates for a syn-Elimination Reaction catalysed by Methylaspartase.
Archer, Catherine H.,Thomas, Neil R.,Gani, David
, p. 1141 - 1152 (2007/10/02)
Methylaspartase catalyses the slow syn-elimination of ammonia from the (2S,3R)--diastereomer of the natural substrate, (2S,3S)-3-methylaspartic acid, to give mesaconic acid.To provide material of sufficient stereochemical purity to probe the mechanism of the reaction, two synthetic routes to (2S,3R)- and (2S,3R)2H>- 3-methylaspartic acid were devised.The use of these (2S,3R)-3-methylaspartic acids revealed that the enzymic reaction does not involve C-3 epimerisation followed by normal anti-elimination, ruling-out the possibility of a carbanion intermediate.Conversely, the substrate displayed very large primary deuterium isotope effects indicating rate-limiting C-H bond cleavage.
