The di-pi-methane photorearrangement of 2,3-disubstituted benzobarrelenes and benzonorbornadiene - Substituent effects in regioselectivity


Altundas R., Dastan A., Unaldi N., Guven K., Uzun O., Balci M.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, no.3, pp.526-533, 2002 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Publication Date: 2002
  • Journal Name: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.526-533
  • Keywords: benzobarrelene, benzonorbornadiene, di-pi-methane rearrangement, photolysis, POLAR SUBSTITUENTS, PHOTOCHEMISTRY, DERIVATIVES, BROMINATION
  • Middle East Technical University Affiliated: No

Abstract

2,3-Disubstituted benzobarrelene and benzonorbornadiene derivatives 16, 17, and 18, containing electron-withdrawing and electron-donating substituents, have been synthesized and subjected to triplet-sensitized photoisomerization. Methyl 3-methyl-2-benzobarrelenecarboxylate (16) gave two di-pi-methane rearrangement products. However, methyl 3-cyano-2-benzobarrelenecarboxyidte (17) underwent an intramolecular [2(pi) + 2(pi)] cycloaddition reaction, whilst methyl 3cyano-2-benzonorbornadienecarboxylate (18) formed dimer 40. The formation of these products is discussed in terms of the radical stabilizing effect of the substituents and the destabitizing effect on the formation of cyclopropane ring.