A stereoselective radical-mediated hydrogermylation of the protected 5-ethynyluracil nucleosides 1  with trialkyl-, triaryl,- tris(trimethylsilyl)germanes gave (Z)-5-(2-germylvinyl) nucleosides 2   as major products (50-80%). Reaction of the intermediary �-triphenylgermyl vinyl radical with oxygen and fragmentation of the resulting peroxyradical provided also 5-[2-(triphenylgermyl)acetyl] pyrimidine nucleosides 3   in low to moderate yields (10-25%). Thermal isomerization of 3  in MeOH via a four-centered activated complex and subsequent hydrolysis of the resulting O-germyl substituted enol yielded 5-acetyluracil nucleosides in quantitative yield.

Conversion of 5-ethynyluracil nucleosides to 5-(2-germylvinyl) and 5-(2-germylacetyl)uracil nucleosides via hydrogermylation

245th National Meeting (2013)

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