title: Stereoselective construction of an unprecedented 7-8 fused ring system in micrandilactone a by [3,3]-sigmatropic rearrangement.
abstract: The 7-8 bicyclic ring system of micrandilactone A (1) with the required stereochemistry and functional groups was constructed by a Bu3Al-promoted Claisen rearrangement. Computational studies indicated that the exocyclic vinyl ether undergoes a [3,3] sigmatropic process via a chairlike transition state to afford exclusively the Z-double bond in the newly generated 8-membered ring with a high level of chirality transfer.
authors.affiliation: Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Shenzhen Graduate School, Peking University, Beijing 100871, China.
authors.forename: Yan-Dong
authors.initials: YD
authors.lastname: Zhang
authors.forename: Wei-Wu
authors.initials: WW
authors.lastname: Ren
authors.forename: Yu
authors.initials: Y
authors.lastname: Lan
authors.forename: Qing
authors.initials: Q
authors.lastname: Xiao
authors.forename: Kai
authors.initials: K
authors.lastname: Wang
authors.forename: Jie
authors.initials: J
authors.lastname: Xu
authors.forename: Jia-Hua
authors.initials: JH
authors.lastname: Chen
authors.forename: Zhen
authors.initials: Z
authors.lastname: Yang
mesh_terms: D002384:Catalysis; D003500:Cyclization; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification; D015394:Molecular Structure; D010946:Plants, Medicinal / Q000737:chemistry*; D032141:Schisandra / Q000737:chemistry*; D013237:Stereoisomerism; D014315:Triterpenes / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification
chemical_list: D007783:Lactones; D014315:Triterpenes; C476501:micrandilactone A; C521652:rubriflorin A