Allylic azides: synthesis, reactivity, and the Winstein rearrangement

Organic azides are useful synthetic intermediates, which demonstrate broad reactivity. Unlike most organic azides, allylic azides can spontaneously rearrange to form a mixture of isomers. This rearrangement has been named the Winstein rearrangement. Using allylic azides can result in low yields and...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2019-05, Vol.17 (18), p.4406-4429
Main Authors: Carlson, Angela S, Topczewski, Joseph J
Format: Article
Language:English
Subjects:
Allyl Compounds - chemical synthesis
Allyl Compounds - chemistry
Azide
Azides (organic)
Azides - chemical synthesis
Azides - chemistry
Cycloaddition Reaction
Intermediates
Isomerism
Isomers
Literature reviews
Models, Chemical
Oxidation-Reduction
Racemization
Reactivity
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Summary:Organic azides are useful synthetic intermediates, which demonstrate broad reactivity. Unlike most organic azides, allylic azides can spontaneously rearrange to form a mixture of isomers. This rearrangement has been named the Winstein rearrangement. Using allylic azides can result in low yields and azide racemization in some synthetic contexts due to the Winstein rearrangement. Effort has been made to understand the mechanism of the Winstein rearrangement and to take advantage of this process. Several guiding principles can be used to identify which azides will produce a mixture of isomers and which will resist rearrangement. Selective reaction conditions can be used to differentiate the azide isomers in a dynamic manner. This review covers all aspects of allylic azides including their synthesis, their reactivity, the mechanism of the Winstein rearrangement, and reactions that can selectively elaborate an azide isomer. This review covers the literature from Winstein's initial report to early 2019.
ISSN:1477-0520
1477-0539
1477-0539
DOI:10.1039/c8ob03178a