Pull–Pull Halogenated β‐Cyanoacrylates in Aza‐Michael Reaction: Intriguing Problem of Regioselectivity

Abstract The controlled regioselective addition of nitrogen‐centered nucleophiles to the pull–pull halogenated β‐cyanoacrylates is a challenging problem in the chemistry of pull–pull alkenes due to the close electronic properties of the vicinal acceptor groups. The influence of the type of halogen and its position on the double bond, as well as the amine nucleophilicity and the presence of additives on the direction of addition have been studied. The experimental data are in excellent agreement with the density functional theory (DFT) calculations.