TY - DATA T1 - Intramolecular Photocycloaddition Reactions of Arylcyclopropane Tethered 1‑Cyanonaphthalenes PY - 2016/08/22 AU - Hajime Maeda AU - Shoji Matsuda AU - Kazuhiko Mizuno UR - https://acs.figshare.com/articles/journal_contribution/Intramolecular_Photocycloaddition_Reactions_of_Arylcyclopropane_Tethered_1_Cyanonaphthalenes/3793224 DO - 10.1021/acs.joc.6b01721.s002 L4 - https://ndownloader.figshare.com/files/5906364 KW - zwitterionic biradicals KW - 1- cyanonaphthalene ring KW - side chain KW - 4- position KW - arylcyclopropane side chain KW - arylcyclopropane moiety KW - 10π conrotatory ring opening KW - novel nine-membered ring products KW - Intramolecular Photocycloaddition Reactions KW - photocycloadduct KW - intramolecular exciplex mechanism KW - photoreaction KW - 1- cyanonaphthalenes KW - CH 3 CN KW - cyanoarene ring KW - fluorescence investigations KW - 2- position KW - photoinduced intramolecular electron transfer pathway N2 - Intramolecular photocycloaddition reactions of 1-cyanonaphthalenes bearing an arylcyclopropane containing side chain were investigated. Photoreactions of members of this family in which the arylcyclopropane moiety is bonded at the 2-position of the 1-cyanonaphthalene ring produce head-to-head and head-to-tail 1,2-[3+2] photocycloadducts. On the other hand, substances in this family containing an arylcyclopropane side chain linked to the 4-position of the cyanoarene ring undergo photoreactions to form [4+3] photocycloadducts along with novel nine-membered ring products, which are produced by photochemically induced 10π conrotatory ring opening of the initially formed intramolecular [3+2] cycloadducts. The results of solvent effects and fluorescence investigations along with those focusing on corresponding intermolecular photoreactions demonstrate that the photocycloadducts are formed predominantly through an intramolecular exciplex mechanism and that a photoinduced intramolecular electron transfer pathway via zwitterionic biradicals might be partly responsible for the process when CH3CN is the solvent. ER -