In:
Canadian Journal of Chemistry, Canadian Science Publishing, Vol. 83, No. 9 ( 2005-09-01), p. 1492-1509
Abstract:
The origin of the HERON reaction is reviewed from a historical perspective and shown to have its foundation in the unusual properties of bisheteroatom-substituted amides, so-called anomeric amides. The reaction involves migration of anomerically destabilized oxo-substituents on an amide nitrogen to the amide carbon and dissociation of the amide bond. Computational work providing a theoretical basis for the reaction is presented, together with physical organic measurements that support results therefrom. The rearrangement has been observed in a number of chemical transformations of N-alkoxy-N-aminoamides, reactions of 1-acyloxy-1-alkoxydiazenes, N-alkoxy-N-aminocarbamates, N-alkoxyhydroxamic acids, as well as in the gas-phase reactions of N-acyloxy-N-alkoxyamides.Key words: HERON reaction, anomeric amides, rearrangements, hindered esters, concerted reactions.
Type of Medium:
Online Resource
ISSN:
0008-4042
,
1480-3291
Language:
English
Publisher:
Canadian Science Publishing
Publication Date:
2005
detail.hit.zdb_id:
1482256-8
Bookmarklink