Theoretical evidence for oxygenated intermediates in the reductive cyclization of nitrobenzenes

Davies I. W., Guner V., Houk K.

Organic Letters, cilt.6, sa.5, ss.743-746, 2004 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 6 Sayı: 5
  • Basım Tarihi: 2004
  • Doi Numarası: 10.1021/ol0364273
  • Dergi Adı: Organic Letters
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.743-746
  • Hacettepe Üniversitesi Adresli: Evet

Özet

Deoxygenation of nitroaromatics is a classic synthetic method for the construction of nitrogen heterocycles. The generally accepted mechanism involves exhaustive deoxygenation to a singlet nitrene. We present theoretical evidence for an alternative, 6π-electron 5-atom electrocyclization of nitroso-styrenes, -stilbenes, and -biphenyls to nitronates. A downstream 1,5-H shift and tautomerization leads to N-hydroxy heterocycles.