4753-03-1Relevant academic research and scientific papers
2′-Alkynylnucleotides: A Sequence- and Spin Label-Flexible Strategy for EPR Spectroscopy in DNA
Haugland, Marius M.,El-Sagheer, Afaf H.,Porter, Rachel J.,Pe?a, Javier,Brown, Tom,Anderson, Edward A.,Lovett, Janet E.
supporting information, p. 9069 - 9072 (2016/08/05)
Electron paramagnetic resonance (EPR) spectroscopy is a powerful method to elucidate molecular structure through the measurement of distances between conformationally well-defined spin labels. Here we report a sequence-flexible approach to the synthesis of double spin-labeled DNA duplexes, where 2′-alkynylnucleosides are incorporated at terminal and internal positions on complementary strands. Post-DNA synthesis copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions with a variety of spin labels enable the use of double electron-electron resonance experiments to measure a number of distances on the duplex, affording a high level of detailed structural information.
Synthesis of pyrimidine 2′-deoxy ribonucleosides branched at the 2′-position via radical atom-transfer cyclization reaction with a vinylsilyl group as a radical-acceptor tether
Sukeda,Shuto,Sugimoto,Ichikawa,Matsuda
, p. 8988 - 8996 (2007/10/03)
Recently, we developed a regio- and stereoselective method for introducing a vinyl group at the position β to a hydroxyl group in halohydrins or α-phenylselenoalkanols via a radical atom-transfer cyclization reaction with a vinylsilyl group as a temporary connecting radical-acceptor tether. The synthesis of 2′-deoxy-2′-C-vinyl- and 2′-deoxy-2′-C-hydroxymethyluridines (7 and 8, respectively) and the corresponding 2′-deoxycytidine congeners (10 and 11, respectively), which were designed as potential antitumor and/or antiviral agents, was achieved using this radical atom-transfer cyclization as the key step. When the 2′-deoxy-2′-iodo-5′-O-monomethoxytrityl (MMTr) uridine derivative 19a, bearing a vinylsilyl group at the 3′-hydroxyl group, was heated with (Me3Sn)2 and AIBN in benzene, the corresponding radical atom-transfer product was generated, which in turn was successively treated with tetrabutylammonium fluoride and TBSCI/imidazole to give the desired 2′-deoxy-5′-O-MMTr-3′-O-TBS-2′-C-vinyluridine (25). Compound 25 was successfully converted into the target 2′-deoxy-2′-branched pyrimidine ribonucleosides 7, 8, 10, and 11.
Nucleic acid related compounds. 91. Biomimetic reactions are in harmony with loss of 2'-substituents as free radicals (not anions) during mechanism-based inactivation of ribonucleotide reductases. Differential interactions of azide, halogen, and alkylthio
Robins, Morris J.,Wnuk, Stanislaw F.,Hernández-Thirring, Amelia E.,Samano, Mirna C.
, p. 11341 - 11348 (2007/10/03)
The initial step in the mechanism-based inactivation of ribonucleotide reductases by 2'-chloro-2'deoxynucleotides is abstraction of H3' by a proximal free radical on the enzyme. The C3' radical is postulated to undergo spontaneous loss of chloride, and th
