Abstract An asymmetric aldol reaction using Oppolzer's sultam has provided a practical and efficient synthetic route (15 steps, overall yield ca. 24%) to 12 compounds of the Antimycin A family and deisovalerylblastmycin, which were obtained in pure form on a 60–300 mg scale. In the syntheses, the nine-membered dilactone ring was constructed successfully by lactonization of a 2-pyridinethiol ester bearing a TIPS group on the 8-OH by using the ( ...