Our recent progress on the intramolecular Diels-Alder reaction approach in natural products synthesis: synthetic studies of the octahydronaphthalene substructure of versipelostatins and the A/B/C-tricyclic substructure of GKK1032s.

During this decade, the enantio- and stereoselective synthesis of natural products has been actively explored in the author's laboratory. In this account, the author outlines practical syntheses of the polycyclic substructures of two novel structurally formidable antibiotics, namely, the trans-fused octahydronaphthalene moiety of versipelostatins and the A/B/C-tricyclic decahydrofluorene moiety of GKK1032s. Both syntheses have been achieved with remarkable regio- and stereoselectivity via intramolecular Diels-Alder reactions using well-designed enantiomeric substrates.