Ring splitting of azetidin-2-ones via radical anions
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 alpha-cleavage...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2012 |
| País: | España |
| Institución: | Universitat Politècnica de València (UPV) |
| Repositorio: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia |
| Idioma: | inglés |
| OAI Identifier: | oai:riunet.upv.es:10251/61121 |
| Acceso en línea: | https://riunet.upv.es/handle/10251/61121 |
| Access Level: | acceso abierto |
| Palabra clave: | POLARIZABLE CONTINUUM MODEL BETA-LACTAM RING N-(ARYLIDENE(OR ALKYLIDENE)AMINO)-2-AZETIDINONES STEREOCONTROLLED SYNTHESIS STEREOSELECTIVE-SYNTHESIS PHOTOCHEMICAL-REACTIONS BUILDING-BLOCKS DNA PHOTOLYASE VINYL ETHERS AZETIDINES QUIMICA ORGANICA |
| Sumario: | 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 alpha-cleavage. The preference for beta-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. |
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