Evidence for a Sigmatropic and an Ionic Pathway in the Winstein Rearrangement

Amy A. Ott, Mary H. Packard, Manuel A. Ortuno, Alayna Johnson, Victoria P. Suding, Christopher J. Cramer, Joseph J. Topczewski

Research output: Contribution to journalArticle

11 Scopus citations


The spontaneous rearrangement of allylic azides is thought to be a sigmatropic reaction. Presented herein is a detailed investigation into the rearrangement of several allylic azides. A combination of experiments including equilibrium studies, kinetic analysis, density functional theory calculations, and selective 15N-isotopic labeling are included. We conclude that the Winstein rearrangement occurs by the assumed sigmatropic pathway under most conditions. However, racemization was observed for some cyclic allylic azides. A kinetic analysis of this process is provided, which supports a previously undescribed ionic pathway.

Original languageEnglish (US)
Pages (from-to)8214-8224
Number of pages11
JournalJournal of Organic Chemistry
Issue number15
StatePublished - Aug 3 2018

PubMed: MeSH publication types

  • Journal Article
  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

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