A modular total synthesis of aculeatins A, B, E, F and 6-epi-aculeatins E, F

The total synthesis of aculeatins A, B, E and F confirming the assigned absolute configuration of recently isolated aculeatins E and F is documented. A convergent approach has been designed by the addition of both the terminal units (phenol and side chain) at an advanced stage. The central 1,3,5-triol unit with the requisite stereochemistry was prepared from the commercially available α-d-glucoheptonic-γ-lactone. Selective O-debenzylation during the hydrogenolysis of the diyne intermediate and the one pot phenolic oxidation with concomitant spiroketalization highlight the accomplished total syntheses.