6533b7dafe1ef96bd126e325

RESEARCH PRODUCT

Ring splitting of azetidin-2-ones via radical anions

Miguel A. MirandaLuis R. DomingoJosé Antonio López SáezRaúl Pérez-ruizM. Consuelo Jiménez

subject

AnionsAZETIDINESFree RadicalsUltraviolet RaysElectronVINYL ETHERSRing (chemistry)PhotochemistryBiochemistryPolarizable continuum modelchemistry.chemical_compoundN-(ARYLIDENE(OR ALKYLIDENE)AMINO)-2-AZETIDINONESQUIMICA ORGANICAMoietyReactivity (chemistry)BETA-LACTAM RINGPhysical and Theoretical ChemistryTriethylamineDNA PHOTOLYASEMolecular StructureSTEREOCONTROLLED SYNTHESISOrganic ChemistryTransition stateSTEREOSELECTIVE-SYNTHESISchemistryPOLARIZABLE CONTINUUM MODELExcited stateQuantum TheoryPHOTOCHEMICAL-REACTIONSBUILDING-BLOCKS

description

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.

yearjournalcountryeditionlanguage
2012-08-30
10.1039/c2ob26528ahttps://hdl.handle.net/10251/61121