title: The reactions of nitrogen heterocycles with acrolein: scope and prebiotic significance.
abstract: It has been suggested that life began with a self-replicating RNA molecule. However, after much research into the prebiotic synthesis of RNA, the difficulties encountered have lead some to hypothesize that RNA was preceded by a simpler molecule, one more easily synthesized prebiotically. Many of the proposed alternative molecules are based on acrolein, since it reacts readily with nucleophiles, such as the nucleobases, via Michael addition and is readily synthesized from formaldehyde and acetaldehyde. Reports regarding the reactions of nucleobases with concentrated acrolein solutions suggest that this is a plausible reaction mechanism, though there are also reports that the "incorrect" isomers are obtained. The scope and kinetics of the reaction of acrolein with various nitrogen heterocycles are reported here. Reactions of pyrimidines often give N(1) adducts as the major products. Reactions of purines often give N(9) adducts in good yield. The reactions are rapid under neutral to slightly alkaline conditions, and proceed at low temperatures and dilutions. The implications of these findings for the origin of life are discussed.
authors.affiliation: University of California, San Diego and The Scripps Institution of Oceanography, La Jolla, California 92093, USA. hcleaves@ucsd.edu
authors.forename: H James
authors.initials: HJ
authors.lastname: Cleaves
mesh_terms: D000171:Acrolein / Q000737:chemistry*; D000181:Acrylonitrile / Q000737:chemistry; D000447:Aldehydes / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D009584:Nitrogen / Q000737:chemistry*; D000069497:Origin of Life; D011687:Purines / Q000737:chemistry; D011743:Pyrimidines / Q000737:chemistry; D012313:RNA / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D013696:Temperature
chemical_list: D000447:Aldehydes; D011687:Purines; D011743:Pyrimidines; D012313:RNA; D000171:Acrolein; D000181:Acrylonitrile; D009584:Nitrogen