title: Total Synthesis of (-)-Daphenylline.
abstract: Total synthesis of (-)-daphenylline, a hexacyclic Daphniphyllum alkaloid, was achieved. Construction of the tricyclic DEF ring system was initiated by asymmetric Negishi coupling followed by an intramolecular Friedel-Crafts reaction. Installation of a side chain onto the tricyclic core was carried out through Sonogashira coupling, stereocontrolled Claisen rearrangement by taking advantage of the characteristic conformation of the tricyclic DEF core, and the stereoselective alkylation of a lactone. After the introduction of a glycine unit, the ABC ring system was stereoselectively constructed through intramolecular cycloaddition of the cyclic azomethine ylide.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8601, Japan.
authors.forename: Ryosuke
authors.initials: R
authors.lastname: Yamada
authors.affiliation: Graduate School of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
authors.forename: Yohei
authors.initials: Y
authors.lastname: Adachi
authors.affiliation: Graduate School of Pharmaceutical Sciences, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8601, Japan. yokosima@ps.nagoya-u.ac.jp.
authors.forename: Satoshi
authors.initials: S
authors.lastname: Yokoshima
authors.affiliation: Graduate School of Pharmaceutical Sciences, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8601, Japan. fukuyama@ps.nagoya-u.ac.jp.
authors.forename: Tohru
authors.initials: T
authors.lastname: Fukuyama
keywords: alkaloids; cycloaddition; natural products; rearrangement; stereoselective synthesis