Theoretical evidence for oxygenated intermediates in the reductive cyclization of nitrobenzenes

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

Organic Letters, vol.6, no.5, pp.743-746, 2004 (SCI-Expanded, Scopus) identifier identifier

  • Publication Type: Article / Article
  • Volume: 6 Issue: 5
  • Publication Date: 2004
  • Doi Number: 10.1021/ol0364273
  • Journal Name: Organic Letters
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.743-746
  • Hacettepe University Affiliated: Yes

Abstract

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.