title: Unified strategy to monoterpene indole alkaloids: total syntheses of (±)-goniomitine, (±)-1,2-dehydroaspidospermidine, (±)-aspidospermidine, (±)-vincadifformine, and (±)-kopsihainanine A.
abstract: Total syntheses of (±)-goniomitine, (±)-1,2-dehydroaspidospermidine, (±)-aspidospermidine, (±)-vincadifformine, and (±)-kopsihainanine A were achieved featuring two common key steps: (1) a palladium-catalyzed decarboxylative vinylation that provides quick access to cyclopentene intermediates containing all of the carbons present in the natural products and (2) an integrated oxidation/reduction/cyclization (iORC) sequence for skeletal reorganization that converts the cyclopentenes to the pentacyclic structures of the natural products. By incorporation of a geometric constraint to iORC substrates, both the chemoselectivity (C7 vs N1 cyclization) and the stereoselectivity (trans- vs cis-fused ring system) of the cyclization process can be controlled.
authors.affiliation: Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne , EPFL-SB-ISIC-LSPN, BCH5304, CH-1015 Lausanne, Switzerland.
authors.forename: Olivier
authors.initials: O
authors.lastname: Wagnières
authors.forename: Zhengren
authors.initials: Z
authors.lastname: Xu
authors.forename: Qian
authors.initials: Q
authors.lastname: Wang
authors.forename: Jieping
authors.initials: J
authors.lastname: Zhu
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis; D001688:Biological Products / Q000138:chemical synthesis; D060326:Chemistry Techniques, Synthetic; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis; D026121:Indole Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry*; D039821:Monoterpenes / Q000737:chemistry*; D011804:Quinolines / Q000138:chemical synthesis
chemical_list: D000470:Alkaloids; D001688:Biological Products; D006576:Heterocyclic Compounds, 4 or More Rings; D026121:Indole Alkaloids; D039821:Monoterpenes; D011804:Quinolines; C409672:aspidospermidine; C526621:goniomitine; C562138:kopsihainanine A; C456406:vincadifformine