jo026440l_si_001.pdf (2.08 MB)
Photochemical Reactivity of 1-Substituted-1-aza-1,4-dienes Promoted by Electron-Acceptor Sensitizers. Di-π-methane Rearrangements and Alternative Reactions via Radical-Cation Intermediates
journal contribution
posted on 2002-11-23, 00:00 authored by Diego Armesto, Maria J. Ortiz, Antonia R. Agarrabeitia, Santiago Aparicio-Lara, Mar Martin-Fontecha, Marta Liras, M. Paz Martinez-AlcazarIrradiation of a series of β,γ-unsaturated imines, oxime acetates, and oxime methyl ethers, using
9,10-dicyanoanthrathene (DCA) or dicyanodurene (DCD) as electron acceptor sensitizers, affords
the corresponding cyclopropanes resulting from 1-aza-di-π-methane rearrangements via radical
cations. In some cases, alternative reactions of these intermediates occur to yield nitriles,
dihydroquinolines, dihydronaphthalene derivatives, and cycloaddition products. Some of these
products result from reactions via alkene radical-cation intermediates while others arise by
pathways involving imine radical-cation intermediates. The yields of products formed in these
processes were significantly higher when DCD was used as electron-acceptor sensitizer instead of
DCA.