Enantioselective halogenative semi-pinacol rearrangement: a stereodivergent reaction on a racemic mixture

An efficient, quantitative deracemization strategy for optically inactive allylic cycloalkanols has been achieved using the biphasic halogenative semi-pinacol reaction protocol. The resultant beta-halo spiroketones, containing three contiguous stereogenic centers, were easily recovered with high diastereomeric and enantiomeric purities following conventional silica gel chromatography. The optically active products could be further manipulated chemically, affording synthetically interesting scaffolds with complete preservation of stereoisomeric integrity.