title: An organometallic route to oligonucleotides containing phosphoroselenoate.
abstract: Unlike the widespread use of phosphorothioates in nucleic acid chemistry, complementary research on phosphoroselenoates has been severely limited. Previous routes to DNA and RNA that contain phosphoroselenoates employ elemental Se and KSeCN as Se transfer agents, although these reagents suffer from low or unselective reactivity. The metastability of the Pbond;Se bond demands soluble, selective Se transfer reagents. The organometallic reagent (iPrC(5)H(4))(2)TiSe(5) satisfies these criteria, as we demonstrate by the synthesis of phosphoroselenoate derivatives of mono- and oligonucleotides of DNA and a dinucleotide of RNA. The new general method is compatible with high-throughput phosphoramidate oligonucleotide synthesis, which allows for the preparation of site-specifically labeled oligonucleotides. A (31)P NMR spectroscopy study shows that the phosphoroselenoate of (5')-d(GGAATGTC(Se)TGTCG)-(3') selectively binds to soft Cd(2+) ions but not Mg(2+) ions.
authors.affiliation: Department of Chemistry University of Illinois 601 S. Goodwin Avenue, Urbana, IL 61801 USA.
authors.forename: Geoffrey A
authors.initials: GA
authors.lastname: Holloway
authors.forename: Caroline
authors.initials: C
authors.lastname: Pavot
authors.forename: Stephen A
authors.initials: SA
authors.lastname: Scaringe
authors.forename: Yi
authors.initials: Y
authors.lastname: Lu
authors.forename: Thomas B
authors.initials: TB
authors.lastname: Rauchfuss
mesh_terms: D002413:Cations, Divalent / Q000737:chemistry; D019906:Nuclear Magnetic Resonance, Biomolecular; D009841:Oligonucleotides / Q000138:chemical synthesis*; D009942:Organometallic Compounds / Q000737:chemistry*; D012643:Selenium / Q000737:chemistry*
chemical_list: D002413:Cations, Divalent; D009841:Oligonucleotides; D009942:Organometallic Compounds; D012643:Selenium