Abstract: | A stereoisomer of the natural product and not himastatin, an unusual dimeric depsipeptide with promising antibiotic and antitumor properties, was obtained from pyrroloindoline anti-cis- 1 . This result led to a revision of the proposed stereostructure. The new stereostructure was confirmed by the total synthesis, which involves stereoselective access to the pyrroloindoline syn-cis- 1 and the 5-hydroxypiperazic acid subunit and features a Stille coupling for the formation of the central carbon–carbon bond. |