Radical Truce-Smiles reactions on an isoxazole template: scope and limitations

Research output: Contribution to journalArticle

  • External authors:
  • Srood Rashid
  • Sultan Almadhhi
  • David Berrisford
  • James Raftery
  • Inigo Vitorica-Yrezabal
  • George Whitehead

Abstract

The use of TiCl3-HCl as promotor in the radical Truce-Smiles reactions of 2-(((3,5-dimethylisoxazol-4-yl)sulfonyl)oxy)benzenediazonium salts has been investigated in detail. During these reactions the desired Truce-Smiles rearrangement (via an ipso-substitution reaction) is accompanied by the formation of a number of by-products including dihydrobenzo[5,6][1,2]oxathiino[3,4-d]isoxazole 4,4-dioxides, dioxidobenzo[e][1,2]oxathiin-3-yl)ethan-1-ones, anilines and chloroaromatics. Replacing TiCl3-HCl by Cu(NO3)2-Cu2O as reductant in these reactions was found to afford broadly comparable product distributions. Competition and radical clock experiments also provide an indication of the relative susceptibility of the isoxazole nucleus towards attack by aryl radicals.

Bibliographical metadata

Original languageEnglish
JournalTetrahedron
Early online date14 Mar 2019
DOIs
Publication statusPublished - 2019