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Asymmetric Formal Synthesis of Azadirachtin
Author(s) -
Mori Naoki,
Kitahara Takeshi,
Mori Kenji,
Watanabe Hidenori
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201507935
Subject(s) - chemistry , stereochemistry , moiety , total synthesis , azadirachtin , hemiacetal , radical cyclization , formal synthesis , lactone , cyclopentenone , intramolecular force , tandem , ring (chemistry) , organic chemistry , materials science , pesticide , agronomy , composite material , biology
An asymmetric formal synthesis of azadirachtin, a potent insect antifeedant, was accomplished in 30 steps to Ley’s synthetic intermediate (longest linear sequence). The synthesis features: 1) rapid access to the optically active right‐hand segment starting from the known 5‐hydroxymethyl‐2‐cyclopentenone scaffold; 2) construction of the B and E rings by a key intramolecular tandem radical cyclization; 3) formation of the hemiacetal moiety in the C ring through the α‐oxidation of the six‐membered lactone followed by methanolysis.