Intramolecular photocycloaddition reactions of 2- and 4-(5-arylpent-4-enyl)-1-cyanonaphthalenes

• Published in: Journal of photochemistry and photobiology. A, Chemistry. Vol. 374; pp. 173 - 184
• Main Authors: Maeda, Hajime, Enya, Kouhei, Negoro, Naoki, Mizuno, Kazuhiko
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 01.04.2019; Elsevier BV
• Subjects: Benzene; Benzophenone; Biradical; Derivatives; di-π-methane rearrangement; Exciplex; Intermediates; Irradiation; Naphthalene; Photocycloaddition; Photosensitization; Radiation; Stereoisomers; Triquinane; Exciplex; Photocycloaddition; Triquinane; di-π-methane rearrangement; Biradical
• ISSN: 1010-6030; 1873-2666
• DOI: 10.1016/j.jphotochem.2019.01.033

[Display omitted] •[2 + 2], [3 + 2], and [4 + 2] Photocycloadditions selectively proceeded.•Intramolecular π-π interaction in exciplexes governed the reaction modes.•Di-π-methane rearrangement of [4 + 2] photocycloadducts gave angular triquinanes. Photoreactions of 1-cyanonaphthalene derivatives containing 5-arylpent-4-enyl groups at C-2 or C-4 of the naphthalene ring were investigated. Photoreactions of C-2 derivatives in benzene or CH3CN generated intramolecular [2 + 2] and [3 + 2] photocycloadducts. Substances bearing electron-rich and electron-poor phenyl groups produced respective [2 + 2] and [3 + 2] photocycloadducts preferentially. In contrast, photoreactions of C-4 linked 1-cyanonaphthalenes produced intramolecular [4 + 2] photocycloadducts as main products along with stereoisomers of tricyclic compounds as minor products. The formation of [4 + 2] photocycloadducts was promoted by using benzophenone or Michler's ketone triplet photosensitization, and quenched by O2 or ferrocene. Intramolecular singlet exciplexes, which serve as important intermediates in the mechanistic pathways for these reactions, governed the site-selectivities in photoreactions of both of the 2- and 4-(5-arylpent-4-enyl)-1-cyanonaphthalenes. In addition, [4 + 2] photocycloadducts were observed to undergo di-π-methane rearrangement under irradiation conditions to produce angular triquinane derivatives.