Racemic alpha'-acetoxy alpha,beta-unsaturated cyclohexanone has been converted to the corresponding enantiomerically enriched alpha'-hydroxylated and acetoxylated compounds with 97% ee via enzymatic resolution with PLE. OSO4-Catalyzed dihydroxylation of enantiomerically enriched alpha'-acetoxylated compound afforded a single diastereomer in 85% chemical yield. The absolute configuration of 2,3,6-triacetoxycylohexanone was determined by X-ray diffraction analysis. Subsequent Luche reduction allowed us to obtain corresponding syn-type cyclitol precursors in a highly stereoselective manner as expected. (c) 2006 Elsevier Ltd. All rights reserved.