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

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5 Citations (Scopus)

Abstract

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
Volume83
Issue number15
DOIs
StatePublished - Aug 3 2018

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Azides
Kinetics
Labeling
Density functional theory
Experiments

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Evidence for a Sigmatropic and an Ionic Pathway in the Winstein Rearrangement. / Ott, Amy A.; Packard, Mary H.; Ortuno, Manuel A.; Johnson, Alayna; Suding, Victoria P.; Cramer, Christopher J.; Topczewski, Joseph J.

In: Journal of Organic Chemistry, Vol. 83, No. 15, 03.08.2018, p. 8214-8224.

Research output: Contribution to journalArticle

Ott, Amy A. ; Packard, Mary H. ; Ortuno, Manuel A. ; Johnson, Alayna ; Suding, Victoria P. ; Cramer, Christopher J. ; Topczewski, Joseph J. / Evidence for a Sigmatropic and an Ionic Pathway in the Winstein Rearrangement. In: Journal of Organic Chemistry. 2018 ; Vol. 83, No. 15. pp. 8214-8224.
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