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Issue 43, 2013
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Reversal of facial selectivity in a thia-Claisen rearrangement by incorporation of a vinylic bromine substituent

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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.

Graphical abstract: Reversal of facial selectivity in a thia-Claisen rearrangement by incorporation of a vinylic bromine substituent

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Publication details

The article was received on 01 Aug 2013, accepted on 25 Sep 2013 and first published on 26 Sep 2013


Article type: Paper
DOI: 10.1039/C3OB41580E
Citation: Org. Biomol. Chem., 2013,11, 7530-7539
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    Reversal of facial selectivity in a thia-Claisen rearrangement by incorporation of a vinylic bromine substituent

    A. R. Ellwood, A. J. P. Mortimer, J. M. Goodman and M. J. Porter, Org. Biomol. Chem., 2013, 11, 7530
    DOI: 10.1039/C3OB41580E

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