Ellwood, AR;
Mortimer, AJP;
Goodman, JM;
Porter, MJ;
(2013)
Reversal of facial selectivity in a thia-Claisen rearrangement by incorporation of a vinylic bromine substituent.
ORGANIC & BIOMOLECULAR CHEMISTRY
, 11
(43)
7530 - 7539.
10.1039/c3ob41580e.
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Abstract
Thia-Claisen rearrangements have been carried out using N-benzylpyrrolidine-2-thione and chiral allylic bromides derived from D-mannitol. Introduction of a bromine atom onto the double bond of the allylic bromide reverses the sense of diastereoselectivity in the [3,3]-sigmatropic rearrangement. Density functional theory calculations lead us to rationalise the observed selectivity in terms of a Cíeplak effect.
| Type: | Article |
|---|---|
| Title: | Reversal of facial selectivity in a thia-Claisen rearrangement by incorporation of a vinylic bromine substituent |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1039/c3ob41580e |
| Publisher version: | http://dx.doi.org/10.1039/c3ob41580e |
| Additional information: | © The Royal Society of Chemistry 2013. This Open Access Article is licensed under a Creative Commons Attribution 3.0 Unported Licence. PubMed ID: 24091642 |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/1410347 |
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