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 Diego Armesto Maria J. Ortiz Antonia R. Agarrabeitia Santiago Aparicio-Lara Mar Martin-Fontecha Marta Liras M. Paz Martinez-Alcazar 10.1021/jo026440l.s001 https://acs.figshare.com/articles/journal_contribution/Photochemical_Reactivity_of_1-Substituted-1-aza-1_4-dienes_Promoted_by_Electron-Acceptor_Sensitizers_Di-_-methane_Rearrangements_and_Alternative_Reactions_via_Radical-Cation_Intermediates/3696720 Irradiation 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. 2002-11-23 00:00:00 dihydronaphthalene derivatives products result DCD imine DCA Alternative Reactions Photochemical Reactivity oxime methyl ethers oxime acetates intermediate cycloaddition products electron acceptor sensitizers alternative reactions