title: Production of tartrates by cyanide-mediated dimerization of glyoxylate: a potential abiotic pathway to the citric acid cycle.
abstract: An abiotic formation of meso- and DL-tartrates in 80% yield via the cyanide-catalyzed dimerization of glyoxylate under alkaline conditions is demonstrated. A detailed mechanism for this conversion is proposed, supported by NMR evidence and (13)C-labeled reactions. Simple dehydration of tartrates to oxaloacetate and an ensuing decarboxylation to form pyruvate are known processes that provide a ready feedstock for entry into the citric acid cycle. While glyoxylate and high hydroxide concentration are atypical in the prebiotic literature, there is evidence for natural, abiotic availability of each. It is proposed that this availability, coupled with the remarkable efficiency of tartrate production from glyoxylate, merits consideration of an alternative prebiotic pathway for providing constituents of the citric acid cycle.
authors.affiliation: School of Chemical and Biological Engineering and ‡School of Chemistry and Biochemistry, Georgia Institute of Technology , Atlanta, Georgia 30332, United States.
authors.forename: Christopher
authors.initials: C
authors.lastname: Butch
authors.forename: Elizabeth D
authors.initials: ED
authors.lastname: Cope
authors.forename: Pamela
authors.initials: P
authors.lastname: Pollet
authors.forename: Leslie
authors.initials: L
authors.lastname: Gelbaum
authors.forename: Ramanarayanan
authors.initials: R
authors.lastname: Krishnamurthy
authors.forename: Charles L
authors.initials: CL
authors.lastname: Liotta
mesh_terms: D002952:Citric Acid Cycle; D003486:Cyanides / Q000737:chemistry*; D019281:Dimerization; D006038:Glyoxylates / Q000737:chemistry*; D015394:Molecular Structure; D013644:Tartrates / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D003486:Cyanides; D006038:Glyoxylates; D013644:Tartrates; C031150:glyoxylic acid
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