Johns, Jennifer P; van Losenoord, Arjan; Mary, Clement; Garcia, Pierre; Pankhurst, Damian; Rosser, Adam Andrew; Glover, Stephen

Author(s)

Johns, Jennifer P

van Losenoord, Arjan

Mary, Clement

Garcia, Pierre

Pankhurst, Damian

Rosser, Adam Andrew

Glover, Stephen

Publication Date

2010

Abstract

The HERON reaction has been observed in the thermal decompositions of N-acyloxy-N-alkoxyamides 1b, members of the class of anomeric amides. The N,N-bisoxo-substitution results in reduced amide resonance and this, combined with an nₒ–σ*NOAcyl anomeric destabilization of the N–OAcyl bond, results in their intramolecular rearrangement to anhydrides 42 and alkoxynitrenes 43 in competition with homolysis of the N–OAcyl bond to alkoxyamidyls 51. The primary HERON product alkoxynitrenes are scavenged by oxygen, giving a nitrate ester, in competition with a rearrangement to nitriles and dimerization to hyponitrites, leading, under the conditions, to alcohols and aldehydes. Persistent alkoxyamidyls most likely form a 1,3-diradical in a solvent-cage reaction, which cyclizes to 3,5-disubstituted-(5H)-1,4,2-dioxazoles 47. Substituent effects support this competition reaction.

Citation

Australian Journal of Chemistry, 63(12), p. 1717-1729

ISSN

1445-0038

0004-9425

Link

https://hdl.handle.net/1959.11/7321

Publisher

CSIRO Publishing

Title

Thermal Decomposition of N-Acyloxy-N-alkoxyamides: a New HERON Reaction

Type of document

Journal Article

Entity Type

Publication

Author(s)	Johns, Jennifer P van Losenoord, Arjan Mary, Clement Garcia, Pierre Pankhurst, Damian Rosser, Adam Andrew Glover, Stephen
Publication Date	2010
Abstract	The HERON reaction has been observed in the thermal decompositions of N-acyloxy-N-alkoxyamides 1b, members of the class of anomeric amides. The N,N-bisoxo-substitution results in reduced amide resonance and this, combined with an nₒ–σ*NOAcyl anomeric destabilization of the N–OAcyl bond, results in their intramolecular rearrangement to anhydrides 42 and alkoxynitrenes 43 in competition with homolysis of the N–OAcyl bond to alkoxyamidyls 51. The primary HERON product alkoxynitrenes are scavenged by oxygen, giving a nitrate ester, in competition with a rearrangement to nitriles and dimerization to hyponitrites, leading, under the conditions, to alcohols and aldehydes. Persistent alkoxyamidyls most likely form a 1,3-diradical in a solvent-cage reaction, which cyclizes to 3,5-disubstituted-(5H)-1,4,2-dioxazoles 47. Substituent effects support this competition reaction.
Citation	Australian Journal of Chemistry, 63(12), p. 1717-1729
ISSN	1445-0038 0004-9425
Link	https://hdl.handle.net/1959.11/7321
Publisher	CSIRO Publishing
Title	Thermal Decomposition of N-Acyloxy-N-alkoxyamides: a New HERON Reaction
Type of document	Journal Article
Entity Type	Publication

Thermal Decomposition of N-Acyloxy-N-alkoxyamides: a New HERON Reaction

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