Regio- and Stereochemistry of [2+2] Photocycloadditions of Imines to Alkenes: A Computational and Experimental Study

  1. Sampedro, D. 1
  2. Soldevilla, A. 1
  3. Campos, P.J. 1
  4. Ruiz, R. 1
  5. Rodríguez, M.A. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

Revista:
Journal of Organic Chemistry

ISSN: 0022-3263

Año de publicación: 2008

Volumen: 73

Número: 21

Páginas: 8331-8336

Tipo: Artículo

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DOI: 10.1021/JO8015242 SCOPUS: 2-s2.0-55249106894 WoS: WOS:000260533300024 GOOGLE SCHOLAR

Otras publicaciones en: Journal of Organic Chemistry

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Resumen

(Chemical Equation Presented) The [2 + 2] photocycloaddition of isoxazolines to alkenes has been studied by means of CASPT2/6-31G*// CASSCF/6-31G*. The reaction outcome is influenced by the relative ratio of imine deactivation and photocycloaddition. Analysis of the conical intersection points involved in the photoreaction shows that fast deactivation is prevented when an electron-withdrawing group is placed in any position that can affect the imine moiety. Computational data predict that the photoreaction will be regiospecific but without stereoselectivity. Furthermore, the favored regioisomer will be different for alkenes with electron-withdrawing or electron-releasing substituents. The results of a complementary experimental study correlate well with the computational data. Several conclusions included in the present work could prove useful for the generalization of the photocycloaddition of imines. © 2008 American Chemical Society.