Adam R. Ellwood, Anne J. Price Mortimer, Jonathan M. Goodman and Michael J. Porter
Org. Biomol. Chem., 2013,11, 7530-7539
DOI:
10.1039/C3OB41580E,
Paper
Open Access Learn more..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.
