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Intramolecular Photocycloaddition Reactions of Arylcyclopropane Tethered 1‑Cyanonaphthalenes

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journal contribution
posted on 2016-08-22, 00:00 authored by Hajime Maeda, Shoji Matsuda, Kazuhiko Mizuno
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.

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