title: Exploratory experiments on the chemistry of the "glyoxylate scenario": formation of ketosugars from dihydroxyfumarate.
abstract: In the context of a "glyoxylate scenario" of primordial metabolism, the reactions of dihydroxyfumarate (DHF) with reactive small molecule aldehydes (e.g., glyoxylate, formaldehyde, glycolaldehyde, and glyceraldehyde) in water were investigated and shown to form dihydroxyacetone, tetrulose, and the two pentuloses, with almost quantitative conversion. The practically clean and selective formation of ketoses in these reactions, with no detectable admixture of aldoses, stands in stark contrast to the formose reaction, where a complex mixture of linear and branched aldoses and ketoses are produced. These results suggest that the reaction of DHF with aldehydes could constitute a reasonable pathway for the formation of carbohydrates and allow for alternative potential prebiotic scenarios to the formose reaction to be considered.
authors.affiliation: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Rd, La Jolla, California 92037, USA.
authors.forename: Vasudeva Naidu
authors.initials: VN
authors.lastname: Sagi
authors.forename: Venkateshwarlu
authors.initials: V
authors.lastname: Punna
authors.forename: Fang
authors.initials: F
authors.lastname: Hu
authors.forename: Geeta
authors.initials: G
authors.lastname: Meher
authors.forename: Ramanarayanan
authors.initials: R
authors.lastname: Krishnamurthy
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis / Q000737:chemistry; D005650:Fumarates / Q000138:chemical synthesis / Q000737:chemistry*; D006038:Glyoxylates / Q000138:chemical synthesis / Q000737:chemistry*; D007661:Ketoses / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000447:Aldehydes; D005650:Fumarates; D006038:Glyoxylates; D007661:Ketoses; C005998:dihydroxyfumarate