Heteroatom Rearrangements On Nitrogen (HERON) reactions were first identified in the early nineties and named at the second HERON Island Conference on reactive intermediates and unusual molecules. The earliest examples involved decomposition of N-alkoxy-N-aminoamides to esters and 1,1-diazenes [1], the outcome of the instability of these highly pyramidalised bisheteroatom-substituted amides.

First published as a named reaction in 1995 [2], it is now listed in 13th edition of the Merck Index. Since that time, a number of other examples of this rearrangement have been identified including thermal decomposition of N,N'-diacyl-N,N'-dialkoxyamides to esters [3], rearrangement of N-alkoxy-N-azidoamides, which is an excellent source of highly hindered esters [4], reactions of azodicarboxylates with oxygen nucleophiles and, more recently, reactions of the mutagens, N-acyloxy-N-alkoxyamides, in the gas phase during ESI-MS and upon thermolysis in solution. The rearrangement now has a firm theoretical basis from B3LYP/6-31G* calculations [3, 4] and X-ray analysis of HERON precursors has confirmed the highly atypical properties of "HERON" amides, which have sp³ hybridised nitrogens [5]. The reaction was recently the subject of a Can. J. Chem. review [6].

This paper will describe the origin of the reaction, its theoretical basis and ensuing the applications.

[1] J. J. Campbell, S. A. Glover, J. Chem. Res. (S) 1999, 8, 474-475.

[2] J. M. Buccigross, S. A. Glover, J. Chem. Soc. Perkin Trans. 2 1995, 595-603.

[3] S. A. Glover, G. Mo, A. Rauk, Tetrahedron 1999, 55, 3413-3426.

[4] S. A. Glover, G. Mo, J. Chem. Soc. Perkin Trans. 2 2002, 1728-1739.

[5] A.-M. E. Gillson, S. A. Glover, D. J. Tucker, P. Turner, Org. Biomol. Chem. 2003, 1, 3430-3437.

[6] S. A Glover, A. Rauk, J. M. Buccigross, J. J. Campbell, G. A. Hammond, G. Mo, L. E. Andrews, A.-M., E. Gillson, Can. J. Chem. 2005, 83, 1492-1509.

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