Orthoquinone monoketal chemistry. Experimental and density functional theory studies on orthoquinol acetate rearrangements

Stéphane Quideau, Matthew A. Looney, Laurent Pouységu, Sihyun Ham, David M. Birney

Research output: Contribution to journalArticle

47 Scopus citations

Abstract

The non-dimerizing orthoquinone monoketal, 6-acetoxy-6-methoxy-3- methoxycarbonylcyclohexa-2,4-dienone, conveniently prepared from oxidative acetoxylation of its parent phenol with PhI(OAc)2 in CH2Cl2-AcOH (3:1), cleanly undergoes 1,3-acetoxy migrations in the presence of silica gel at room temperature to furnish a 60:40 product mixture conceivably derived from [3,5] and [3,3] sigmatropic rearrangements. Density functional theory calculations indicate that the [3,5] shift is pseudopericyclic, has a remarkably low activation energy of 20.1 kcal/mol, and is favored by 5.4 kcal/mol over the pericyclic [3,3] shift, in qualitative agreement with the experimental observations.

Original languageEnglish
Pages (from-to)615-618
Number of pages4
JournalTetrahedron Letters
Volume40
Issue number4
DOIs
StatePublished - Jan 22 1999

Keywords

  • Dimerization
  • Oxidation
  • Quinonoid compounds
  • Rearrangements

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