Total Synthesis of (−)‐Daphenylline. Issue 20 (8th April 2016)

• Record Type: Journal Article
• Authors: Yamada, Ryosuke; Adachi, Yohei; Yokoshima, Satoshi; Fukuyama, Tohru
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 20(2016)
• Page Start: 6067
• Page End: 6070
• Publication Date: 2016-04-08
• Subjects: alkaloids -- cycloaddition -- natural products -- rearrangement -- stereoselective synthesis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201601958
• Languages: English
• ISSNs: 1433-7851

Abstract

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. Abstract : Ring ring ring : Total synthesis of daphenylline, a hexacyclic Daphniphyllum alkaloid, was achieved. The synthesis features a remote stereocontrolled Claisen rearrangement that takes advantage of the characteristic conformation of the tricyclic DEF core, and intramolecular cycloaddition of a cyclic azomethine ylide to simultaneously construct the ABC ring system.