Synchronized aromaticity as an enthalpic driving force for the aromatic cope rearrangement

David J. Babinski, Xiaoguang Bao, Marie El Arba, Bo Chen, David A. Hrovat, Weston Thatcher Borden, Doug E. Frantz

Research output: Contribution to journalArticle

20 Scopus citations

Abstract

We report herein experimental and theoretical evidence for an aromatic Cope rearrangement. Along with several successful examples, our data include the first isolation and full characterization of the putative intermediate that is formed immediately after the initial [3,3] sigmatropic rearrangement. Calculations at the B3LYP/6-31G(d) level of theory predict reaction energy barriers in the range 22-23 kcal/mol for the [3,3]-rearrangement consistent with the exceptionally mild reaction conditions for these reactions. The experimental and computational results support a significant enthalpic contribution of the concomitant pyrazole ring formation that serves as both a kinetic and thermodynamic driving force for the aromatic Cope rearrangement.

Original languageEnglish (US)
Pages (from-to)16139-16142
Number of pages4
JournalJournal of the American Chemical Society
Volume134
Issue number39
DOIs
StatePublished - Oct 3 2012

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Babinski, D. J., Bao, X., El Arba, M., Chen, B., Hrovat, D. A., Borden, W. T., & Frantz, D. E. (2012). Synchronized aromaticity as an enthalpic driving force for the aromatic cope rearrangement. Journal of the American Chemical Society, 134(39), 16139-16142. https://doi.org/10.1021/ja307213m