A highly stereoselective formal total synthesis of the ornithine decarboxylase inhibitors (-)-saliniketals A and B is described. The salient features of the synthesis are the utilization of a desymmetrization technique to create six contiguous chiral centers from a single bicyclic precursor as well as substrate-controlled Grignard reaction, intramolecular Wacker-type oxidation, and antialdol reaction following Pirrung-Heathcock conditions.

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Enantioselective and a highly concise total synthesis of Ambrisentan are described. The chiral auxiliary controlled enantioselective epoxidation (Azerad protocol), photochemical regioselective epoxide opening, and base mediated ester hydrolysis reactions are the key reactions.

The asymmetric total synthesis of okaspirodiol was achieved following Sharpless asymmetric epoxidation, Gilman reaction, Wittig reaction, Horner–Wadsworth–Emmons olefination, and coupling of alkyne with the aldehyde, and acid‐catalyzed spiroketalization as key reactions.