Development of the HERON Reaction: A Historical Account

Title
Development of the HERON Reaction: A Historical Account
Publication Date
2017
Author(s)
Glover, Stephen
( author )
OrcID: https://orcid.org/0000-0002-9344-8669
Email: sglover@une.edu.au
UNE Id une-id:sglover
Type of document
Journal Article
Language
en
Entity Type
Publication
Publisher
CSIRO Publishing
Place of publication
Australia
DOI
10.1071/ch16683
UNE publication id
une:21140
Abstract
This account describes the discovery and development of the HERON reaction, a reaction with special connection to the Heron Island Conferences on Reactive Intermediates and Unusual Molecules. This modern 'named' reaction describes an unusual rearrangement of bisheteroatom-substituted amides RCON(X)(Y) whereby the more electron deficient group, X, migrates from nitrogen to the carbonyl carbon giving an acyl derivative, RC(O)X, and Y-stabilised nitrenes. In it, the origins, mechanistic elucidation, and theoretical validation are described in more or less chronological order. Along that time line we introduce the concepts of 'anomeric amides', 'amidicity' in anomeric amides, and their role in the HERON reaction. All known versions of the reaction that have since been discovered are outlined and a basic understanding of the relative roles of reduced resonance and the anomeric driving force, both functions of the heteroatom substituents at the amide nitrogen, are quantified.
Link
Citation
Australian Journal of Chemistry, 70(4), p. 344-361
ISSN
1445-0038
0004-9425
Start page
344
End page
361

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