Theoretical evidence for oxygenated intermediates in the reductive cyclization of nitrobenzenes
Organic Letters, vol.6, no.5, pp.743-746, 2004 (SCI-Expanded, Scopus)
- 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.