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Total Synthesis of (−)‐Daphenylline
Author(s) -
Xu Bo,
Wang Bingyang,
Xun Wen,
Qiu Fayang G.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201902268
Subject(s) - intramolecular force , total synthesis , chemistry , annulation , aromatization , stereoselectivity , stereochemistry , ring (chemistry) , amide , yield (engineering) , organic chemistry , catalysis , materials science , metallurgy
A concise and highly stereoselective total synthesis of the Daphniphyllum alkaloids (−)‐daphenylline has been accomplished. The synthesis was started from ( S )‐carvone and proceeded via a stereoselective Mg(ClO 4 ) 2 ‐catalyzed intramolecular amide addition cyclization, an intramolecular Diels–Alder reaction to construct the ABCD tetracyclic core architecture, and a Robinson annulation coupled with an oxidative aromatization sequence. Finally, the DF ring system was installed through an intramolecular Friedel–Crafts cyclization. The total synthesis of (−)‐daphenylline is achieved in 19 steps in the longest reaction sequence and in 7.6 % overall yield.