A convenient approach to modify bioactive substrates such as daunorubicin, cytisine, and camphecene with a pentafluorosulfanylvinyl moiety have been suggested. F5S-CH = CH derivatives of daunorubicin were obtained by acylation with reactive 4-nitrophenyl-4-(pentafluoro-lambda(6)-sulfanyl)alkenyl carbonates, while the corresponding conjugates of anthracycline antibiotic daunorubicin, alkaloid cytisine and camphecene were synthesized using a click chemistry procedure.