A method of producing 4'-O-alkyl and 4'-O-aralkyl derivatives of anthracyclines of Formula, wherein: R 1 is H, OH or OMe; R 2 is H, OH or OCOAlk1, with Alk1 being selected from the group consisting of linear or branched C 1 -C 12 alkyl, linear or branched C 1 C 12 alkenyl and linear or branched C 1 -C 12 alkynyl; 4'-OCH 2 -R 3 is equatorial or axial, where R 3 is H, Alk1 or Ar, with Alk1 being defined as above, and Ar being selected from where R 4 to R 8 are independently selected from the group consisting of hydrogen, linear or branched C 1 -C 5 alkyl, linear or branched C 1 -C 5 alkenyl and linear or branched C 1 -C 5 alkynyl, F, Cl, and CF 3; and An is an anion of a strong acid; the method comprising the steps of: (a) providing a derivative of daunorubicin hydrochloride of Formula with R 1 being defined as above, being dissolved in an alcohol (b) incubating the daunorubicin hydrochloride of step (a) with trifluoromethanesulfonyl azide until complete reaction, to produce 3'-N 3 -daunorubicin of Formula, with R 1 being defined as above (c) dissolving the 3'-N 3 -daunorubicin of step (b) in an aprotic solvent and reacting with an excess of an alkylating agent R 3 CH 2 X and a strong base, to produce 4'-OCH 2 R 3 -3'-N 3 -daunorubicin of Formula, wherein R 1 and R 3 are defined as above, and X is selected from the group consisting of Cl -, Br -, I -, tosyl (Ts) and CH 3 SO 2 O-CF 3 SO 2 O (d) dissolving the 4'-OCH 2 R 3 -3'-N 3 -daunorubicin of step (c) in tetrahydrofuran and reacting it with triphenylphosphine, to produce 4'-OCH 2 R 3 -daunorubicin of Formula, with R 1 and R 3 being defined as above (e) reacting the 4'-OCH 2 R 3 -daunorubicin of step (d) with a complex halogenide of Formula in an aprotic solvent, to produce a 14-halogenated derivative where R 9 to R 14 are independently selected from the group consisting of hydrogen and a C 1 -C 4 hydrocarbon radical; and Hal - is Cl, Br or I; and (f) hydrolyzing the 14-halogenated derivative of step (e) in the presence of carboxylic acid salts, to produce the 4'-O-alkyl or 4'-O-aralkyl derivative of Formula, wherein R 2 is OH or OC(=O)Alk1. R 1 is H, OH or OMe; R 2 is H, OH or OCOAlk1, with Alk1 being selected from the group consisting of linear or branched C 1 -C 12 alkyl, linear or branched C 1 C 12 alkenyl and linear or branched C 1 -C 12 alkynyl; 4'-OCH 2 -R 3 is equatorial or axial, where R 3 is H, Alk1 or Ar, with Alk1 being defined as above, and Ar being selected from where R 4 to R 8 are independently selected from the group consisting of hydrogen, linear or branched C 1 -C 5 alkyl, linear or branched C 1 -C 5 alkenyl and linear or branched C 1 -C 5 alkynyl, F, Cl, and CF 3; and An is an anion of a strong acid; the method comprising the steps of: (a) providing a derivative of daunorubicin hydrochloride of Formula with R 1 being defined as above, being dissolved in an alcohol (b) incubating the daunorubicin hydrochloride of step (a) with trifluoromethanesulfonyl azide until complete reaction, to produce 3'-N 3 -daunorubicin of Formula, with R 1 being defined as above (c) dissolving the 3'-N 3 -daunorubicin of step (b) in an aprotic solvent and reacting with an excess of an alkylating agent R 3 CH 2 X and a strong base, to produce 4'-OCH 2 R 3 -3'-N 3 -daunorubicin of Formula, wherein R 1 and R 3 are defined as above, and X is selected from the group consisting of Cl -, Br -, I -, tosyl (Ts) and CH 3 SO 2 O-CF 3 SO 2 O (d) dissolving the 4'-OCH 2 R 3 -3'-N 3 -daunorubicin of step (c) in tetrahydrofuran and reacting it with triphenylphosphine, to produce 4'-OCH 2 R 3 -daunorubicin of Formula, with R 1 and R 3 being defined as above (e) reacting the 4'-OCH 2 R 3 -daunorubicin of step (d) with a complex halogenide of Formula in an aprotic solvent, to produce a 14-halogenated derivative where R 9 to R 14 are independently selected from the group consisting of hydrogen and a C 1 -C 4 hydrocarbon radical; and Hal - is Cl, Br or I; and (f) hydrolyzing the 14-halogenated derivative of step (e) in the presence of carboxylic acid salts, to produce the 4'-O-alkyl or 4'-O-aralkyl derivative of Formula, wherein R 2 is OH or OC(=O)Alk1. (a) providing a derivative of daunorubicin hydrochloride of Formula with R 1 being defined as above, being dissolved in an alcohol (b) incubating the daunorubicin hydrochloride of step (a) with trifluoromethanesulfonyl azide until complete reaction, to produce 3'-N 3 -daunorubicin of Formula, with R 1 being defined as above (c) dissolving the 3'-N 3 -daunorubicin of step (b) in an aprotic solvent and reacting with an excess of an alkylating agent R 3 CH 2 X and a strong base, to produce 4'-OCH 2 R 3 -3'-N 3 -daunorubicin of Formula, wherein R 1 and R 3 are defined as above, and X is selected from the group consisting of Cl -, Br -, I -, tosyl (Ts) and CH 3 SO 2 O-CF 3 SO 2 O (d) dissolving the 4'-OCH 2 R 3 -3'-N 3 -daunorubicin of step (c) in tetrahydrofuran and reacting it with triphenylphosphine, to produce 4'-OCH 2 R 3 -daunorubicin of Formula, with R 1 and R 3 being defined as above (e) reacting the 4'-OCH 2 R 3 -daunorubicin of step (d) with a complex halogenide of Formula in an aprotic solvent, to produce a 14-halogenated derivative where R 9 to R 14 are independently selected from the group consisting of hydrogen and a C 1 -C 4 hydrocarbon radical; and Hal - is Cl, Br or I; and (f) hydrolyzing the 14-halogenated derivative of step (e) in the presence of carboxylic acid salts, to produce the 4'-O-alkyl or 4'-O-aralkyl derivative of Formula, wherein R 2 is OH or OC(=O)Alk1.