Published in Henry Rzepa's Blog

A reader asked me about the mechanism of the reaction of 2-picoline N-oxide with acetic anhydride to give 2-acetoxymethylpyridine (the Boekelheide Rearrangement[cite]10.1002/ejoc.201000936[/cite]). He wrote “ I don’t understand why the system should prefer to go via fragmentation-recombination (… the evidence being that oxygen labelling shows scrambling) when there is an easy concerted pathway available (… a

References

Organic ChemistryPhysical and Theoretical Chemistry

A New Sequential Intramolecular Cyclization Based on the Boekelheide Rearrangement

Published in European Journal of Organic Chemistry
Authors Assunta Massaro, Alessandro Mordini, Anna Mingardi, Jens Klein, Daniele Andreotti

AbstractPyrrolidines and piperidines were synthesized from (aminoalkyl)pyridine N‐oxides with a general and quite efficient method developed by using di‐tert‐butylsilyl bis(trifluoromethanesulfonate) as a new promoter for a Boekelheide‐type reaction. The use of a new Boekelheide promoter, which is compatible with amino groups, opens new perspectives in view of its application in intramolecular cyclizations.