Please use this identifier to cite or link to this item: https://hdl.handle.net/1959.11/7321
Title: Thermal Decomposition of N-Acyloxy-N-alkoxyamides: a New HERON Reaction
Contributor(s): Johns, Jennifer P (author); van Losenoord, Arjan (author); Mary, Clement (author); Garcia, Pierre (author); Pankhurst, Damian  (author); Rosser, Adam Andrew  (author)orcid ; Glover, Stephen  (author)orcid 
Publication Date: 2010
DOI: 10.1071/CH10350
Handle Link: https://hdl.handle.net/1959.11/7321
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.
Publication Type: Journal Article
Source of Publication: Australian Journal of Chemistry, 63(12), p. 1717-1729
Publisher: CSIRO Publishing
Place of Publication: Australia
ISSN: 1445-0038
0004-9425
Fields of Research (FoR) 2008: 030501 Free Radical Chemistry
030505 Physical Organic Chemistry
030503 Organic Chemical Synthesis
Socio-Economic Objective (SEO) 2008: 970103 Expanding Knowledge in the Chemical Sciences
Peer Reviewed: Yes
HERDC Category Description: C1 Refereed Article in a Scholarly Journal
Appears in Collections:Journal Article
School of Science and Technology

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