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Full Paper
Towards the Total Synthesis of Mycaperoxide B: Probing Biosynthetic Rationale
Article first published online: 27 DEC 2011
DOI: 10.1002/ejoc.201101477
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Silva, E. M. P., Pye, R. J., Brown, G. D. and Harwood, L. M. (2012), Towards the Total Synthesis of Mycaperoxide B: Probing Biosynthetic Rationale. Eur. J. Org. Chem., 2012: 1209–1216. doi: 10.1002/ejoc.201101477
Publication History
- Issue published online: 13 FEB 2012
- Article first published online: 27 DEC 2011
- Manuscript Received: 11 OCT 2011
Funded by
- Portuguese Foundation for Science and Technology. Grant Number: SFRH/BPD/66961/2009
Keywords:
- Natural products;
- Biomimetic synthesis;
- Michael addition;
- Peroxides;
- Oxygen heterocycles
Abstract
Studies towards the biomimetic synthesis of mycaperoxide B (1) are described. We have established the synthesis of four diastereoisomers of mycaperoxide B methyl ester (1a) by employing a Michael addition across an α,β-unsaturated ester precursor 2 as the key step. This result strongly suggestsstereocontrol in the addition of the hydroperoxide functionality to the E double bond and discloses the importance of choosing the correct geometry of the α,β-unsaturated double bond when attempting to synthesise mycaperoxide B. Four diastereoisomeric tetrahydrofurans derived from an intramolecular rearrangement of the 1,2-dioxolane enolate 12 were also isolated and characterised.