Palladium hydroxide catalyzed isomerization of primary allylic alcohols to aldehydes: application to the formal synthesis of (-)-brevisamide.

The Pd-catalyzed isomerization of primary allylic alcohols into the corresponding saturated aldehydes has been achieved at room temperature for the first time in good to excellent yields under mild conditions. The functional group compatibility in this reaction is studied, and this new methodology has been successfully applied in the synthesis of a C5-C13 tetrahydropyran ring system of (-)-brevisamide in seven steps.