A series of 3,4-dimethoxyphenylethylamine derivatives was prepared from Baylis–Hillman (BH) adducts. The effect of these compounds on the proliferation of breast cancer cell lines (MCF-7) and the corresponding Doxorubicin (Dox) resistant cell lines (MCF-7/ADR) was studied. Aminoalcohols 1a–d were obtained from the Michael addition reaction of 3,4-dimethoxyphenylethylamine and BH adducts. For the preparation of unsaturated amines 2a–d, BH adducts were converted into allylic bromides by treatment with HBr in acidic solution.N-nucleophile introduction could be controlled by the choice of solvent furnishing the corresponding amines 2a–d. A third class of amines (3a–c) was prepared by hydrogenation reaction of amines 2a–d. In respect of the biological evaluation, some of the synthesized compounds exhibited moderate inhibitory effect on the cell growth. In addition, in MCF-7/ADR cell lines, the antiproliferative effect of Dox shifted from 5 to 88 % when co-administrated with compound 2b.