The Absolute Configuration of the Pyrrolosesquiterpenoid Glaciapyrrol A

✍ Scribed by Ramona Riclea; Dr. Jeroen S. Dickschat

• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 273 KB
• Volume: 17
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.201101139

✦ Synopsis

Abstract

The total syntheses of the structurally unique and moderately cytotoxic pyrrolosesquiterpenoid glaciapyrrol A that has been isolated from a marine streptomycete by Macherla et al.1 and of seven of its stereoisomers have been performed from geraniol or nerol, respectively, using a known diastereoselective Ru‐catalysed approach for the synthesis of tetrahydrofurans previously reported by Stark and co‐workers.5 Comparison of ^1^H and ^13^C NMR data unambiguously clarified the relative configuration of natural glaciapyrrol A that was previously only partly solved from the available NMR data. An enantioselective synthesis was carried out resulting in the unnatural enantiomer (11__S__,12__R__,15__R__)‐(−)‐glaciapyrrol A. These data establish the absolute configuration of the natural product as (11__R__,12__S__,15__S__)‐(+)‐glaciapyrrol A.