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, sa.3, ss.526-533, 2002 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Basım Tarihi: 2002
  • Dergi Adı: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.526-533
  • Anahtar Kelimeler: benzobarrelene, benzonorbornadiene, di-pi-methane rearrangement, photolysis, POLAR SUBSTITUENTS, PHOTOCHEMISTRY, DERIVATIVES, BROMINATION
  • Atatürk Üniversitesi Adresli: Evet

Özet

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.