The reaction of electrochemically generated N-acyliminium ion pools with alkenes bearing a heteroatom nucleophilic functionality such as a hydroxy group, a carboxy group, and an oxime moiety led to intermolecular carbon carbon bond formation followed by intramolecular carbon heteroatom bond formation to give the corresponding heterocyclic compounds such as cyclic ethers, lactones, and 2-isoxazolines, respectively.