title: Peptide Bond Formation in Water Mediated by Carbon Disulfide.
abstract: Demonstrating plausible nonenzymatic polymerization mechanisms for prebiotic monomers represents a fundamental goal in prebiotic chemistry. While a great deal is now known about the potentially prebiotic synthesis of amino acids, our understanding of abiogenic polymerization processes to form polypeptides is less well developed. Here, we show that carbon disulfide (CS2), a component of volcanic emission and sulfide mineral weathering, and a widely used synthetic reagent and solvent, promotes peptide bond formation in modest yields (up to ∼20%) from α-amino acids under mild aqueous conditions. Exposure of a variety of α-amino acids to CS2 initially yields aminoacyl dithiocarbamates, which in turn generate reactive 2-thiono-5-oxazolidone intermediates, the thio analogues of N-carboxyanhydrides. Along with peptides, thiourea and thiohydantoin species are produced. Amino acid stereochemistry was preserved in the formation of peptides. Our findings reveal that CS2 could contribute to peptide bond formation, and possibly other condensation reactions, in abiogenic settings.
authors: Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute , La Jolla, California.
authors: Luke J
authors: LJ
authors: Leman
authors: Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute , La Jolla, California.
authors: Zheng-Zheng
authors: ZZ
authors: Huang
authors: Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute , La Jolla, California.
authors: M Reza
authors: MR
authors: Ghadiri
mesh_terms: D000693:Anaerobiosis; D002246:Carbon Disulfide / Q000737:chemistry*; D066241:Carbon-13 Magnetic Resonance Spectroscopy; D002851:Chromatography, High Pressure Liquid; D004151:Dipeptides / Q000737:chemistry*; D066244:Proton Magnetic Resonance Spectroscopy; D021241:Spectrometry, Mass, Electrospray Ionization; D014867:Water / Q000737:chemistry*
chemical_list: D004151:Dipeptides; D014867:Water; D002246:Carbon Disulfide