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Total Synthesis of Limonin
Author(s) -
Yamashita Shuji,
Naruko Akito,
Nakazawa Yuki,
Zhao Le,
Hayashi Yujiro,
Hirama Masahiro
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201503794
Subject(s) - limonin , limonoid , androstane , chemistry , stereochemistry , ring (chemistry) , total synthesis , radical cyclization , cycloaddition , singlet oxygen , tandem , terpene , organic chemistry , oxygen , catalysis , materials science , food science , composite material
Limonoids are highly oxygenated C13α‐triterpenes and common secondary metabolites. Several hundred congeners have been isolated to date. The first total synthesis of (±)‐limonin, the flagship congener of the limonoids, is now reported and features 1) a tandem radical cyclization generating the BCD ring system with the C13α configuration that is essential to the limonoids and a Robinson annulation to construct the limonoid androstane framework, 2) a singlet‐oxygen cycloaddition and a Baeyer–Villiger oxidation to synthesize the highly oxidized D ring, and 3) a Suárez reaction to construct the unique AA′ ring system.