Total Synthesis of Panaxydiol and (−)-Virol C

A direct approach to the total synthesis of panaxydiol (<b>1</b>) and (-)-virol C (<b>2</b>) is reported. This strategy highlights the utility of γ-polyhaloalkylation reactions of siloxydienes in target-directed synthesis, enabling the construction of functionalized conjugated π-systems poised for further manipulation. Titanium-mediated enantioselective transformations enable asymmetric synthesis and identify an unexpected discrepancy in facial selectivity that is resolved by total synthesis.