First total synthesis of antibiotic C104 (1), a prototypical member of the angucyclines, was accomplished. Highly regioselective cycloaddition of α-alkoxybenzyne 12 with angularly fused α-siloxyfuran10 enabled the straightforward construction of the characteristic benz[a]anthraquinone framework. The D-olivosyl C-glycoside was introduced via the O→C-glycoside rearrangement in a regio- and stereoselective manner.