title: Ring splitting of azetidin-2-ones via radical anions.
abstract: The radical anions of azetidin-2-ones, generated by UV-irradiation in the presence of triethylamine, undergo ring-splitting via N-C4 or C3-C4 bond breaking, leading to open-chain amides. This reactivity diverges from that found for the neutral excited states, which is characterised by α-cleavage. The preference for β-cleavage is supported by DFT theoretical calculations on the energy barriers associated with the involved transition states. Thus, injection of one electron into the azetidin-2-one moiety constitutes a complementary activation strategy which may be exploited to produce new chemistry.
authors.affiliation: Departamento de Química/Instituto de Tecnología Química UPV-CSIC, Universitat Politécnica de València, Camino de Vera s/n, 46022, Valencia, Spain.
authors.forename: Raúl
authors.initials: R
authors.lastname: Pérez-Ruiz
authors.forename: Jose A
authors.initials: JA
authors.lastname: Sáez
authors.forename: Luis R
authors.initials: LR
authors.lastname: Domingo
authors.forename: M Consuelo
authors.initials: MC
authors.lastname: Jiménez
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Miranda
mesh_terms: D000838:Anions / Q000737:chemistry; D001384:Azetidines / Q000138:chemical synthesis* / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry; D015394:Molecular Structure; D011789:Quantum Theory; D014466:Ultraviolet Rays
chemical_list: C116379:2-azetidinone; D000838:Anions; D001384:Azetidines; D005609:Free Radicals