title: Unified Total Synthesis of Madangamines A, C, and E.
abstract: A stereodivergent strategy for the synthesis of skipped dienes is developed. The method consists of hydroboration of allenes and Migita-Kosugi-Stille coupling, which allows for access to all four possible stereoisomers of the skipped dienes. The hydroboration is especially useful for providing both E-allylic and Z-allylic alcohols from the same allene by simply changing the organoborane reagent. The strategy was successfully applied to a unified total synthesis of the madangamine alkaloids via a common ABCE-tetracyclic intermediate with a (Z,Z)-skipped diene. The late-stage variation of the D-ring enabled the supply of synthetic madangamines A, C, and E for the first time.
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Technology, Keio University , 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Takahiro
authors.initials: T
authors.lastname: Suto
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Technology, Keio University , 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Yuta
authors.initials: Y
authors.lastname: Yanagita
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Technology, Keio University , 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Yoshiyuki
authors.initials: Y
authors.lastname: Nagashima
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Technology, Keio University , 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Shinsaku
authors.initials: S
authors.lastname: Takikawa
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Technology, Keio University , 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Kurosu
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Technology, Keio University , 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Naoya
authors.initials: N
authors.lastname: Matsuo
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Technology, Keio University , 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Takaaki
authors.identifier: 0000-0001-5769-3408
authors.initials: T
authors.lastname: Sato
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Technology, Keio University , 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
authors.forename: Noritaka
authors.initials: N
authors.lastname: Chida
mesh_terms: D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D006576:Heterocyclic Compounds, 4 or More Rings; C508399:madangamine A; C000627248:madangamine C; C000627249:madangamine E