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

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.

SUBMITTER: Ott AA 

PROVIDER: S-EPMC6076873 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature