| 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 | |
| Language |
en
|
| Publisher |
CSIRO Publishing
|
| Title |
Thermal Decomposition of N-Acyloxy-N-alkoxyamides: a New HERON Reaction
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| Type of document |
Journal Article
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| Entity Type |
Publication
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