title: The absolute configuration of the pyrrolosesquiterpenoid glaciapyrrol A.
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. 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. 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 (11S,12R,15R)-(-)-glaciapyrrol A. These data establish the absolute configuration of the natural product as (11R,12S,15S)-(+)-glaciapyrrol A.
authors: Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany.
authors: Ramona
authors: R
authors: Riclea
authors: Jeroen S
authors: JS
authors: Dickschat
mesh_terms: D000080462:Acyclic Monoterpenes; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D011758:Pyrroles / Q000138:chemical synthesis / Q000737:chemistry* / Q000302:isolation & purification; D012717:Sesquiterpenes / Q000138:chemical synthesis / Q000737:chemistry* / Q000302:isolation & purification; D013237:Stereoisomerism; D013302:Streptomyces / Q000737:chemistry*; D013729:Terpenes / Q000737:chemistry*
chemical_list: D000080462:Acyclic Monoterpenes; D011758:Pyrroles; D012717:Sesquiterpenes; D013729:Terpenes; C501803:glaciapyrrole A; C007836:geraniol