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RESEARCH FRONT
Contents Vol 63(12)

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

Jennifer P. Johns A , Arjan van Losenoord A , Clément Mary A , Pierre Garcia A , Damian S. Pankhurst A , Adam A. Rosser A and Stephen A. Glover A B
+ Author Affiliations
- Author Affiliations

A Department of Chemistry, School of Science and Technology, University of New England, Armidale, NSW 2351, Australia.

B Corresponding author. Email: sglover@une.edu.au

Australian Journal of Chemistry 63(12) 1717-1729 https://doi.org/10.1071/CH10350
Submitted: 23 September 2010  Accepted: 22 October 2010   Published: 6 December 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.


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