A Pauson-Khand approach to the synthesis of ingenol.

[reaction: see text] Pauson-Khand cyclization of dioxanone photoadduct 21 leads to the formation of a single product in good yield. However, retro-aldol fragmentation of the pentacyclic cyclopentenone 22 leads to the formation of 23, with cis C-8/C-10 intrabridgehead stereochemistry, unlike the target compound ingenol 1, which possesses C-8/C-10 trans intrabridgehead stereochemistry.