Pull-pull β-oxo-α- or β-halo enoates: A toy for synthetic and theoretical studies?

Achieving high level of chemo- and regioselectivity has been the Achilles’ heel of organic synthesis. The selectivity of aza-Michael addition to pull-pull β-oxohalo enoates has been studied. Theoretical and synthetic aspects of the selectivity of these reactions are discussed. [Display omitted] •Theoretical studies can accurately predict nucleophilic attacks on pull-pull β-oxo-α- or β-haloenoates as electron-deficient alkenes bearing two acceptor functions in vicinal positions.•Methods for the selective one-pot cascade construction of several privileged aza-heterocycles have been developed.•The assembly of all heterocyclic cores is initiated by aza-Michael reaction.