Rearrangements of tetrahydroimidazo[1,5-b]isoxazole-2,3-dicarboxylates to pyrrolo[1,2-e]imidazol-6-ols, precursors of 2,5-dihydro-1H-pyrrole derivatives

Coskun N., Cetin M.

TETRAHEDRON, vol.65, no.3, pp.648-658, 2009 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 65 Issue: 3
  • Publication Date: 2009
  • Doi Number: 10.1016/j.tet.2008.11.019
  • Journal Name: TETRAHEDRON
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.648-658
  • Bursa Uludag University Affiliated: Yes


Isoxazolines 2 from the cycloaddition of imidazoline 3-oxides 1 with DMAD rearrange in the presence of methoxide to give cis-3-methoxy-7-(methoxycarbonyl)-2,7a-diaryl-5-oxo-2,3,5,7a-tetrahydro-1H-pyrrolo[1,2-e]imidazol-6-olates 3 with 100% de. The acidic hydrolysis of 3 led to kinetically controlled formation of methyl 1-forimyl-4-hydroxy-5-oxo-2-phenyl-2-((arylamino)methyl)-2,5-dihydro-1H-pyrrole-3-carboxylates 6a-e. The intramolecular transformylations of the latter to the Corresponding (E)- and (Z)-methyl 4-hydroxy-2-((N-(aryl)formamido)methyl)-5-oxo-2-phenyl-2,5-dihydro-1H-pyrrole-3-carboxylates 7a-e were shown to be substituent dependent (correlate with sigma) and characterized by Hammett type equations. The effect of temperature was investigated and the rho constants determined for the same reaction series at 50, 60 and 70 degrees C. The amide diastereomeric ratio [(E)-7]/[(Z)-7] is substituent dependent and can be described by the equation log[(E)]/[(Z)](x)=-rho sigma(1)+log[(E)]/[(Z)](x=H). (c) 2008 Elsevier Ltd. All rights reserved.