A new synthetic route to (±)-pancratistatin was devised utilizing β-silyl styrene as a dienophile in the cycloaddition with 3,5-dibromo-2-pyrone. The TMS group incorporated in the cycloadduct permitted a facile elimination process for the eventual installation of the C(1)-OH function. Subsequent transformations including Curtius rearrangement and Bischler-Napieralski reactions completed the total synthesis of (±)-pancratistatin.

New synthetic routes to (±)-α-lycorane and (±)-1-deoxylycorine were exploited. The endo-cycloadduct of 3,5-dibromo-2-pyrone with styrene-type dienophile provided the pivotal intermediate for the syntheses of the titled natural products.