title: Hydrogermylation of 5-ethynyluracil nucleosides: formation of 5-(2-germylvinyl)uracil and 5-(2-germylacetyl)uracil nucleosides.
abstract: A stereoselective radical-mediated hydrogermylation of the protected 5-ethynyluracil nucleosides with trialkyl-, triaryl,- or tris(trimethylsilyl)germanes gave (Z)-5-(2-germylvinyl)uridine, 2'-deoxyuridine, or ara-uridine as major products. Reaction of the β-triphenylgermyl vinyl radical intermediate with oxygen and fragmentation of the resulting peroxyradical provided also 5-[2-(triphenylgermyl)acetyl]pyrimidine nucleosides in low to moderate yields. Thermal isomerization of the latter in MeOH occurred via a four-centered activated complex, and subsequent hydrolysis of the resulting O-germyl substituted enol yielded 5-acetyluracil nucleosides in quantitative yield.
authors: Department of Chemistry and Biochemistry, Florida International University, Miami, Florida 33199, United States.
authors: Yong
authors: Y
authors: Liang
authors: Jean-Philippe
authors: JP
authors: Pitteloud
authors: Stanislaw F
authors: SF
authors: Wnuk
mesh_terms: D015394:Molecular Structure; D009705:Nucleosides / Q000138:chemical synthesis* / Q000737:chemistry*; D014498:Uracil / Q000031:analogs & derivatives / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D009705:Nucleosides; D014498:Uracil
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