title: Unified route to the palmarumycin and preussomerin natural products. Enantioselective synthesis of (-)-preussomerin G.
abstract: The total syntheses of eight members of the palmarumycin family have been achieved, with identification of the absolute stereochemistry for three of these natural products. In addition, the ras-farnesyl transferase inhibitor (-)-preussomerin G has been synthesized, achieving the first enantioselective route for accessing this family of natural products. Highlights of the synthetic work include an asymmetric epoxidation of a cyclic enone in excellent yield and enantiomeric excess and a potentially biomimetic oxidative spirocyclization for the introduction of the bis-spiroketal array unique to the preussomerin natural products.
authors.affiliation: Department of Chemistry, Imperial College of Science, Technology and Medicine, South Kensington, London SW7 2AY, UK. agmb@ic.ac.uk
authors.forename: Anthony G M
authors.initials: AG
authors.lastname: Barrett
authors.forename: Frank
authors.initials: F
authors.lastname: Blaney
authors.forename: Andrew D
authors.initials: AD
authors.lastname: Campbell
authors.forename: Dieter
authors.initials: D
authors.lastname: Hamprecht
authors.forename: Thorsten
authors.initials: T
authors.lastname: Meyer
authors.forename: Andrew J P
authors.initials: AJ
authors.lastname: White
authors.forename: David
authors.initials: D
authors.lastname: Witty
authors.forename: David J
authors.initials: DJ
authors.lastname: Williams
mesh_terms: D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D002851:Chromatography, High Pressure Liquid; D020650:Combinatorial Chemistry Techniques / Q000379:methods*; D003500:Cyclization; D004146:Dioxanes / Q000138:chemical synthesis*; D004791:Enzyme Inhibitors / Q000138:chemical synthesis*; D004852:Epoxy Compounds; D005658:Fungi / Q000737:chemistry; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D009281:Naphthalenes / Q000138:chemical synthesis / Q000737:chemistry; D013141:Spiro Compounds / Q000138:chemical synthesis*; D013237:Stereoisomerism
chemical_list: D001688:Biological Products; D004146:Dioxanes; D004791:Enzyme Inhibitors; D004852:Epoxy Compounds; D006576:Heterocyclic Compounds, 4 or More Rings; D009281:Naphthalenes; D013141:Spiro Compounds; C462860:palmarumycin C12; C462879:palmarumycin C2; C462859:palmarumycin CP2; C410323:preussomerin G; C422643:palmarumycin CP(1)