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

Mo, Guoning; Glover, Stephen

doi:10.1039/B111250N

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

https://hdl.handle.net/1959.11/11592

Language

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

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	https://hdl.handle.net/1959.11/11592
Language	en
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

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

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