The sulfonation of methyl N-trifluoroacetyldaunosaminide (I) with mesyl chloride or with 4-bromophenylsulfonyl chloride in pyridine gives the corresponding 4-O-mesyl derivative (II) or 4-O-(4-bromophenylsulfonyl) derivative (IIa); both compounds by reaction with NaI in refluxing butanone yield the 4-iodo compound (III). The hydrogenation of (III) with H2 over Pd/C in methanol, followed by hydrolysis with hot acetic acid yields 4-deoxy-N-trifluoroacetyldaunosaminide (IV), which is esterified with p-nitrobenzoyl chloride in pyridine affording the corresponding p-nitrobenzoyl ester (V). The reaction of (V) with dry HCl in methylene chloride gives 1,4-dideoxy-N-trifluoroacetyldanosaminide (VI), which is condensed with daunomycinone (VII) by means of silver trifluoromethylsulfonate in methylene chloride and hydrolyzed with NaOH to afford 4'-deoxy-daunomycine (VIII). The bromination of (VIII) with Br2 in methanol-dioxane gives 4'-deoxy-14-bromodaunomycine (IX), which is finally hydrolyzed with aqueous sodium formate.

The sulfonation of methyl N-trifluoroacetyldaunosaminide (I) with mesyl chloride or with 4-bromophenylsulfonyl chloride in pyridine gives the corresponding 4-O-mesyl derivative (II) or 4-O-(4-bromophenylsulfonyl) derivative (IIa); both compounds by reaction with NaI in refluxing butanone yield the 4-iodo compound (III). The hydrogenation of (III) with H2 over Pd/C in methanol, followed by hydrolysis with hot acetic acid yields 4-deoxy-N-trifluoroacetyldaunosaminide (IV), which is esterified with p-nitrobenzoyl chloride in pyridine affording the corresponding p-nitrobenzoyl ester (V). The reaction of (V) with dry HCl in methylene chloride gives 1,4-dideoxy-N-trifluoroacetyldanosaminide (VI), which is condensed with daunomycinone (VII) by means of silver trifluoromethylsulfonate in methylene chloride and hydrolyzed with NaOH to afford 4'-deoxy-daunomycine (VIII). The bromination of (VIII) with Br2 in methanol-dioxane gives 4'-deoxy-14-bromodaunomycine (IX), which is finally hydrolyzed with aqueous sodium formate.

The sulfonation of methyl N-trifluoroacetyldaunosaminide (I) with mesyl chloride or with 4-bromophenylsulfonyl chloride in pyridine gives the corresponding 4-O-mesyl derivative (II) or 4-O-(4-bromophenylsulfonyl) derivative (IIa); both compounds by reaction with NaI in refluxing butanone yield the 4-iodo compound (III). The hydrogenation of (III) with H2 over Pd/C in methanol, followed by hydrolysis with hot acetic acid yields 4-deoxy-N-trifluoroacetyldaunosaminide (IV), which is esterified with p-nitrobenzoyl chloride in pyridine affording the corresponding p-nitrobenzoyl ester (V). The reaction of (V) with dry HCl in methylene chloride gives 1,4-dideoxy-N-trifluoroacetyldanosaminide (VI), which is condensed with daunomycinone (VII) by means of silver trifluoromethylsulfonate in methylene chloride and hydrolyzed with NaOH to afford 4'-deoxy-daunomycine (VIII). The bromination of (VIII) with Br2 in methanol-dioxane gives 4'-deoxy-14-bromodaunomycine (IX), which is finally hydrolyzed with aqueous sodium formate.