Photoinduced Methanol-Incorporated Cyclization of N-(3-Phenylallyl)arenedicarboximides

Article abstract of DOI:10.1021/jo00350a008

Irradiation of trans-N-(3-phenylallyl)arenedicarboximides 1b, 1c, and 1d in methanol-acetonitrile (1/1 v/v) gave methanol-incorporated cyclization products 3a + 3b, 6a + 6b, and 7, respectively.Chemical and spectroscopic evidence for the structure of the products is presented.The photocyclization of 1c predominantly afforded the more sterically crowded product (6a).The suggested reaction mechanism, , involving initial intramolecular electron transfer from the alkenyl moiety to the singlet excited state of the arenedicarboximide moiety, was supported by the examination of the fluorescence spectra, trans-cis isomerization during the cyclization, and the free-energy change associated with the electron transfer (ΔG_et).The calculated spin density of radical anion of naphthalene-1,2-dicarboximide rationalizes the photochemical result of 1c.