6533b857fe1ef96bd12b46e3

RESEARCH PRODUCT

Translocation versus cyclisation in radicals derived from N-3-alkenyl trichloroacetamides

M. Luisa MarinRamón J. ZaragozáJosep BonjochFaïza DiabaMiguel A. Miranda

subject

Models MolecularFree RadicalsDouble bondStereochemistryRadicalSubstituentChromosomal translocationAlkenesBiochemistryPolarizable continuum modelchemistry.chemical_compoundQUIMICA ORGANICAAcetamidesQUIMICA ANALITICASide chainMoleculeTOOLChloroacetatesTrichloroacetic AcidPhysical and Theoretical ChemistryAMIDESchemistry.chemical_classificationMolecular StructureChemistryOrganic ChemistryCOPPER-COMPLEXESCyclizationPOLARIZABLE CONTINUUM MODELDensity functional theory

description

Under radical reaction conditions, two different and competitive reaction pathways were observed for N-(alpha-methylbenzyl)trichloroacetamides with a N-3-cyclohexenyl substituent: 1,4-hydrogen translocation and radical addition to a double bond. However, for radicals with an acyclic alkenyl side chain, the direct cyclisation process was exclusively observed. The dichotomy between translocation and direct radical cyclisation in these substrates has been theoretically studied using density functional theory (DFT) methods at the B3LYP/6-31G** computational level.

yearjournalcountryeditionlanguage
2011-03-23
10.1039/c0ob01228ahttps://doi.org/10.1039/c0ob01228a