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

TETRAHEDRON

卷:75

Article

Rashid, Srood O.^1,2,3  Almadhhi, Sultan S.¹  Berrisford, David J.¹  Raftery, James¹  Vitorica-Yrezabal, Inigo¹  Whitehead, George¹  Quayle, Peter¹ 

[1] Univ Manchester, Sch Chem, Oxford Rd, Manchester M13 9PL, Lancs, England

[2] Univ Sulaimani, Coll Sci, Dept Chem, Sulaimanyah, Kurdistan Regio, Iraq

[3] Komar Univ Sci & Technol, KRC, Sulaimani 46001, Kurdistan Regio, Iraq

关键词: TiCl3;    Truce-Smiles rearrangement;    Biaryl;    Radical chemistry;    Diazonium;   

DOI  :  10.1016/j.tet.2019.03.015

来源: Elsevier

【 摘 要 】

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. (C) 2019 Elsevier Ltd. All rights reserved.

【 授权许可】

Free