A method of synthesizing R1, R2-substituted-4 (ax. or eq.)-OH anthracyclines and their corresponding salts of Formula (1) from daunorubicin or N-Trifluoroacetyl-4- RI - derivatives of daunorubicin, wherein R1 is defined as H, OH, and 4-HO is defined as ax[ial]. The method includes producing N-Trifluoroacetyl daunorubicin and treating the N- Trifluoroacetyldaunorubicin or N-Trifluoroacetyl-4-R1 -derivatives of daunorubicin, wherein R1 is defined as H, OH, with dimethylsulfoxide activated by different acylating agents. The attained intermediate product is then treated with a strong base (ex. tertiary amines) resulting in the 4 -keto-N-Trifluoroacetyl-4-R1 daunorubicin wherein Ri is defined as H, OH, OMe. The 4-keto-N-Trifluoroacetyl-4-R1 - daunorubicin is reacted with a reducing agent, a derivative of a borohydride of an alkaline metal MHBL3 ,to produce N- Trifluoroacetyl-4-epi-4-R1 -daunorubicin. The N-Trifluoroacetyl-4-epi-4-R1 -daunorubicin undergoes hydrolysis in a basic solution to produce a derivate of an anthoacyclin which is halogenized by complex halogenides to form a 14-Hal-derivative. This result is then hydrolyzed by well-known methods in the presence of a formate of an alkaline metal to form the desired final compound.
