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The Synthesis of Azadirachtin: A Potent Insect Antifeedant
Author(s) -
Ley Steven V.,
AbadSomovilla Antonio,
Anderson James C.,
Ayats Carles,
Bänteli Rolf,
Beckmann Edith,
Boyer Alistair,
Brasca Maria G.,
Brice Abigail,
Broughton Howard B.,
Burke Brenda J.,
Cleator Ed,
Craig Donald,
Denholm Alastair A.,
Denton Ross M.,
DurandReville Thomas,
Gobbi Luca B.,
Göbel Michael,
Gray Brian Lawrence,
Grossmann Robert B.,
Gutteridge Claire E.,
Hahn Norbert,
Harding Sarah L.,
Jennens David C.,
Jennens Lynn,
Lovell Peter J.,
Lovell Helen J.,
de la Puente Mary L.,
Kolb Hartmuth C.,
Koot WinJan,
Maslen Sarah L.,
McCusker Catherine F.,
Mattes Amos,
Pape Andrew R.,
Pinto Andrea,
Santafianos Dinos,
Scott James S.,
Smith Stephen C.,
Somers Andrew Q.,
Spilling Christopher D.,
Stelzer Frank,
Toogood Peter L.,
Turner Richard M.,
Veitch Gemma E.,
Wood Anthony,
Zumbrunn Cornelia
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200801103
Subject(s) - azadirachtin , claisen rearrangement , natural product , chemistry , allene , bicyclic molecule , alkylation , stereochemistry , stereoselectivity , total synthesis , ketone , combinatorial chemistry , organic chemistry , biology , pesticide , agronomy , catalysis
We describe in full the first synthesis of the potent insect antifeedant azadirachtin through a highly convergent approach. An O ‐alkylation reaction is used to unite decalin ketone and propargylic mesylate fragments, after which a Claisen rearrangement constructs the central C8C14 bond in a stereoselective fashion. The allene which results from this sequence then enables a second critical carboncarbon bond forming event whereby the [3.2.1] bicyclic system, present in the natural product, is generated via a 5‐ exo ‐radical cyclisation process. Finally, using knowledge gained through our early studies into the reactivity of the natural product, a series of carefully designed steps completes the synthesis of this challenging molecule.