The reaction of 4'-epi-N-trifluoroacetyldaunorubicin (I) with trifluoro methanesulfonic anhydride gives the corresponding 4'-O-triflate (II), which is converted to 4'-deoxy-4'-iodo-N-trifluoroacetyldaunorubicin (III). The hydrolysis of (III) with NaOH affords 4'-deoxy-4'-iododaunorubicin (IV), which is finally brominated with Br2 and hydrolyzed with aqueous sodium formate.