Evidence for a Sigmatropic and an Ionic Pathway in the Winstein Rearrangement
| Autor: | Christopher J. Cramer, Manuel A. Ortuño, Alayna M. Johnson, Victoria P. Suding, Mary H. Packard, Joseph J. Topczewski, Amy A. Ott |
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| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: |
Allylic rearrangement
Azides 010405 organic chemistry Chemistry organic chemicals Organic Chemistry Kinetic analysis Ionic bonding food and beverages Stereoisomerism Sigmatropic reaction 010402 general chemistry 01 natural sciences Article Catalysis 0104 chemical sciences Allyl Compounds Computational chemistry Density functional theory Racemization |
| Popis: | 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 (15)N-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. |
| Databáze: | OpenAIRE |
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