Diastereoselective oxygen to carbon rearrangements of anomerically linked enol ethers and the total synthesis of (+)-(S,S )-(cis-6-methyltetrahydropyran-2-yl)acetic acid, a component of civet
- 10 May 2000
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 1
- No. 15,p. 2385-2394
- https://doi.org/10.1039/b001243m
Abstract
A range of enol ethers, linked via their oxygen atom to the anomeric centre of a pyran ring system, was shown to undergo oxygen to carbon rearrangement upon treatment with a Lewis acid to give the corresponding 2-carbon substituted products. At low temperature, trimethylsilyl trifluoromethanesulfonate catalysed rearrangements of anomerically linked 6-substituted tetrahydropyranyl enol ethers gave selectively the trans-pyranyl ketones, whereas at higher temperatures selective formation of the cis-pyranyl ketones was observed. In a simple application of the methodology the cis-selective rearrangement was used as the key step in a concise total synthesis of a constituent of civet.Keywords
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