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Total Synthesis of (−)‐Daphenylline
Author(s) -
Yamada Ryosuke,
Adachi Yohei,
Yokoshima Satoshi,
Fukuyama Tohru
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201601958
Subject(s) - intramolecular force , chemistry , stereochemistry , sonogashira coupling , ring (chemistry) , side chain , cycloaddition , stereoselectivity , alkylation , total synthesis , tricyclic , organic chemistry , palladium , polymer , catalysis
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.