Synthesis of 8,2'-Methano- and 8,2'-Ethanoadenosines(Nucleosides and Nucleotides. LXV)

  • USUI HIROYUKI
    Faculty of Pharmaceutical Sciences, Hokkaido University
  • UEDA TOHRU
    Faculty of Pharmaceutical Sciences, Hokkaido University

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Description

Treatment of 3', 5'-O-(tetraisopropyldisiloxane-1,3-diyl)-2'-ketoadenosine (1) with methylenetriphenylphosphorane gave the 2'-methylene derivative (2). Hydroxylation of 1 with OsO_4 gave the 2'-hydroxymethyladenosine (4), which was then converted to the 2'-phenylthiomethyl derivative (5). Photocyclization followed by deprotection of the product furnished 8,2'-methanoadenosine (7), and adenosine fixed in a high-anti conformation. Oxidation of a 2'-hydroxyethylideneadenosine with OsO_4 gave the 2'-dihydroxyethyladenosine (10), which was also converted to the 2'-(2-phenylthioethyl) derivative (11). The photocyclization of 11 and successive elimination of the hydroxyl group gave the 8,2'-ethenoadenosine (13). Catalytic hydrogenation and deprotection of 13 afforded 8,2'-ethanoadenosine (15). The circular dichroism spectral features of C-cycloadenosine are discussed.

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