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RESEARCH ARTICLE
Contents Vol 67(3)

Formation and HERON Reactivity of Cyclic N,N-Dialkoxyamides

Stephen A. Glover A B , Adam A. Rosser A , Avat (Arman) Taherpour A and Ben W. Greatrex A
+ 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 67(3) 507-520 https://doi.org/10.1071/CH13557
Submitted: 15 October 2013  Accepted: 27 November 2013   Published: 30 January 2014

Abstract

Cyclic N,N-dialkoxyamides have been made, for the first time, by hypervalent iodine oxidation of β- and γ-hydroxyhydroxamic esters 17, 19, and 21. The fused γ-lactam products, N-butoxy- and N-benzyloxybenzisoxazolones (22a and 22b), are stable while alicyclic γ-lactam and δ-lactam products, 24 and 25, although observable by NMR spectroscopy and ESI-MS are unstable at room temperature, undergoing HERON reactions. The γ-lactam 24 undergoes exclusive ring opening to give a butyl ester-functionalised alkoxynitrene 28. The δ-lactam 25, instead, undergoes a HERON ring contraction to give butyrolactone (27). The structures of model γ- and δ-lactams 6, 7, and 8 have been determined at the B3LYP/6-31G(d) level of theory and the γ-lactams are much more twisted than the acyclic N,N-dimethoxyacetamide (5) resulting in a computed amidicity for 6 of only 25 % that of N,N-dimethylacetamide (3). The HERON reactions of N,N-dimethoxyacetamide (5) and alicyclic models 6 and 8 have been modelled computationally. The facile ring opening of 6 (EA = 113 kJ mol–1) and ring contraction of 8 (EA = 145 kJ mol–1) are predicted well, when compared with the HERON rearrangement of 5 (EA = 178 kJ mol–1).


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