title: Structural revision of (+)-uprolide F diacetate confirmed by asymmetric total synthesis.
abstract: A new structure for the cytotoxic cembranolide uprolide F diacetate (UFD) was proposed, and an enantioselective total synthesis was accomplished to confirm that our revised structure correctly represented the natural UFD and its absolute configuration. Our synthesis features a late-stage, highly efficient, and diastereoselective Nozaki-Hiyama-Kishi macrocyclization (95% yield) and an unexpected reagent-controlled reversible translactonization, which, being the first example within the cembranolide family, might have biogenetic implications and be of great importance to synthetic studies of the α-methylene-γ-lactone-bearing cembranolides.
authors.affiliation: Department of Chemistry, The Hong Kong University of Science and Technology, Clearwater Bay, Kowloon, Hong Kong, China.
authors.forename: Liangyu
authors.initials: L
authors.lastname: Zhu
authors.affiliation: Department of Chemistry, The Hong Kong University of Science and Technology, Clearwater Bay, Kowloon, Hong Kong, China.
authors.forename: Rongbiao
authors.initials: R
authors.lastname: Tong
mesh_terms: D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D001952:Bridged-Ring Compounds; D007783:Lactones; C416984:uprolide F