Total Synthesis of (−)‐Daphenylline |
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| Authors: | Ryosuke Yamada Dr. Yohei Adachi Dr. Satoshi Yokoshima Prof. Tohru Fukuyama |
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| Affiliation: | 1. Graduate School of Pharmaceutical Sciences, Nagoya University, Nagoya, Japan;2. Graduate School of Pharmaceutical Sciences, University of Tokyo, Tokyo, Japan |
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| 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. |
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| Keywords: | alkaloids cycloaddition natural products rearrangement stereoselective synthesis |
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