TY - JOUR
T1 - Evidence for a Sigmatropic and an Ionic Pathway in the Winstein Rearrangement
AU - Ott, Amy A.
AU - Packard, Mary H.
AU - Ortuno, Manuel A.
AU - Johnson, Alayna
AU - Suding, Victoria P.
AU - Cramer, Christopher J.
AU - Topczewski, Joseph J.
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/8/3
Y1 - 2018/8/3
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.joc.8b00961
DO - 10.1021/acs.joc.8b00961
M3 - Article
C2 - 29870252
AN - SCOPUS:85048215746
SN - 0022-3263
VL - 83
SP - 8214
EP - 8224
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 15
ER -