(2R,3S,4S,5R)-5-Hydroxy-2,3,4-tris(phenylmethoxy)-5-[(phenylmethoxy)methyl]-cyclohexanone is used to explore the steric course of 5-epi-valiolone dehydratase in validamycin A biosynthesis. It can also be used to synthesize 1-Silyl-2,6-diketones as versatile intermediates for divergent synthesis of five and six-membered carbocycle cyclitols under radical and anionic conditions.