Novel [2 + 2] Photocycloaddition-Induced Rearrangement of Bichromophoric Naphthalene-Tethered Resorcinol Ethers Norbert Hoffmann* and Jean-Pierre Pete Laboratoire des Re ´ actions Se ´ lectives et Applications,UMR CNRS et Universite ´ de Reims Champagne-Ardenne, UFR Sciences, B.P. 1039, F-51687 REIMS, Cedex 2, France Yoshihisa Inoue* and Tadashi Mori* Photochirogenesis Project, ERATO, JST andDepartment of Molecular Chemistry, Osaka University, 2-1 Yamada-oka, Suita 565-0871, Japan norbert.hoffmann@univ-reims.fr Received December 13, 2001 The first examples of sequential photocycloaddition-rearrangement reactions of naphthalene- tethered resorcinol ethers are described. Bichromophoric aromatic compounds with naphthalene and resorcinol ether moieties were irradiated in the presence/absence of a small amount of acid to give the corresponding cycloaddition-rearrangement products. From the determination of quantum yields, steady-state fluorescence spectral studies, and fluorescence lifetime measurements, the mechanism of this novel photoinduced multistep reaction was elucidated to involve the initial intramolecular exciplex formation, followed by the intramolecular [2 + 2] photocycloaddition between the two aromatic rings and the subsequent acid-catalyzed skeletal rearrangement of the resulting cyclobutane derivative leading to the final products. Introduction Photocycloadditions of aromatic compounds to olefins have been studied extensively, since these reactions provide us with a convenient direct access to various polyfunctionalized compounds in a single step. 1 Among them, the meta-arene photoaddition to olefin, giving rise to [3 + 2] cycloadducts, is reported amply in the litera- ture. 2 It is also known that, depending on the substitution pattern and/or redox potentials of relevant arene and olefin, the major photochemical route can be switched to [2 + 2] cycloaddition or less frequently to [4 + 2] cycloaddition. 3 However, especially in the absence of electron-withdrawing substituents on the aromatic ring, the [2 + 2] cycloaddition products were not always fully characterized in earlier studies, simply because they were obtained as a complex mixture. 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