Hindered ester formation by Sɴ2 azidation of N-acetoxy-N-alkoxyamides and N-alkoxy-N-chloroamides - novel application of HERON rearrangements

Author(s)
Mo, Guoning
Glover, Stephen
Publication Date
2002
Abstract
Treatment of N-acetoxy-N-alkoxyamides or N-alkoxy-N-chloroamides with sodium azide in aqueous acetonitrile results in Sɴ2 displacement of chloride and the formation of reactive N-alkoxy-N-azidoamides. The reaction with N-acetoxy-N-benzyloxybenzamide has been studied kinetically (k294 = 2 L mol⁻¹ s⁻¹) and azidation of N-formyloxy-N-methoxyformamide has been modeled computationally at the pBP/DN*//HF/6-31G* level of theory. The anomeric amides N-alkoxy-N-azidoamides decompose intramolecularly and spontaneously to esters and two equivalents of nitrogen. This extremely exothermic process facilitates the formation, in excellent yields, of highly hindered esters.
Citation
Journal of the Royal Chemical Society: Perkin Transactions 2 (10), p. 1728-1739
ISSN
1364-5471
1472-779X
Link
Publisher
Royal Society of Chemistry
Title
Hindered ester formation by Sɴ2 azidation of N-acetoxy-N-alkoxyamides and N-alkoxy-N-chloroamides - novel application of HERON rearrangements
Type of document
Journal Article
Entity Type
Publication

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