Abstract A stereoselective synthesis of new dipeptide mimetics based on a diazabicycloalkane scaffold is reported. The route starts from enantiomerically pure azabicycloalkenes 1 that are bis (hydroxylated) and coupled N-terminally to a second amino acid. The key step of the reaction sequence is an oxidative cleavage of the resulting dipeptides 5 to give highly functionalised diazabicycloalkanes 6, which can be easily ...