The scope and limitations of radical-mediated 3′-C-substitution of pyrimidine nucleosides was evaluated with 5′-O-(tert-butyldimethylsilyl) thymidine or its tert-butyldiphenylsilyl analogue having thionoester or thionoamide groups at O-3′, including (methylthio) thiocarbonyl,(phenoxy) thiocarbonyl,(pentafluorophenoxy) thiocarbonyl, and (1-imidazolyl) thiocarbonyl. Their reaction with acrylonitrile, methyl acrylate, and allyltributyltin under ...