The addition of the metalated 1,4-dimethoxybenzenes17a-cto the methyl ketone14was investigated in connection with the construction of theC-glycosidic part of nogalamycin. In most reactions, a selectivity towards the undesired (S)-isomer16awas observed. However, the reaction of the lithiated aromate17cwith 14 at low temperatures in THF favored the formation of the desired (R)-alcohol15a(15a:16a= 4.8:1) in accordance with the chelate modelA. The selectivity was considerably enhanced in the addition of the more hindered lithiated naphthalene18yielding the (R)-isomer15bexclusively. Reduction of15bafforded the dimethylamino compound19b, a direct precursor of the CDEF-ring system of nogalamycin.