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RESEARCH ARTICLE
Contents Vol 64(4)

Synthetic and Computational Studies of Acyl Radical Cyclizations with β-Alkoxyacrylates: Formal Synthesis of (±)-Longianone †

Heather M. Aitken A B , Carl H. Schiesser A B and Christopher D. Donner A B C
+ Author Affiliations
- Author Affiliations

A School of Chemistry, The University of Melbourne, Vic. 3010, Australia.

B Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne, Vic. 3010, Australia.

C Corresponding author. Email: cdonner@unimelb.edu.au

Australian Journal of Chemistry 64(4) 409-415 https://doi.org/10.1071/CH10462
Submitted: 17 December 2010  Accepted: 15 February 2011   Published: 18 April 2011

Abstract

An investigation into the cyclization of acyl radicals with mono- and disubstituted β-alkoxyacrylates is described. Ether-tethered acyl radicals, generated directly from the corresponding aldehyde, undergo cyclization to form dioxaspiro heterocyclic systems including 1,7-dioxaspiro[4,4]nonane-4,8-dione and 1,8-dioxaspiro[5,4]decane-5,9-dione. This strategy is applied to a concise formal synthesis of the fungal metabolite longianone. Density functional theory calculations provide insight into the chemistry of the acyl radicals in this study.


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