title: Translocation versus cyclisation in radicals derived from N-3-alkenyl trichloroacetamides.
abstract: Under radical reaction conditions, two different and competitive reaction pathways were observed for N-(α-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.
authors.affiliation: Instituto de Tecnología Química-Departamento de Química (UPV-CSIC), Avda de los Naranjos s/n, E-46022, Valencia, Spain. marmarin@qim.upv.es
authors.forename: M Luisa
authors.initials: ML
authors.lastname: Marin
authors.forename: Ramon J
authors.initials: RJ
authors.lastname: Zaragoza
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Miranda
authors.forename: Faïza
authors.initials: F
authors.lastname: Diaba
authors.forename: Josep
authors.initials: J
authors.lastname: Bonjoch
mesh_terms: D000081:Acetamides; D000475:Alkenes / Q000737:chemistry*; D062845:Chloroacetates; D003500:Cyclization; D005609:Free Radicals / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D014238:Trichloroacetic Acid / Q000138:chemical synthesis
chemical_list: D000081:Acetamides; D000475:Alkenes; D062845:Chloroacetates; D005609:Free Radicals; D014238:Trichloroacetic Acid; C009528:trichloroacetamide