印楝素的合成：一种强效昆虫拒食剂。
The synthesis of azadirachtin: a potent insect antifeedant.
作者信息
Ley Steven V, Abad-Somovilla 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, Durand-Reville 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 Win-Jan, 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
机构信息
Department of Chemistry, University of Cambridge, UK.
出版信息
Chemistry. 2008;14(34):10683-704. doi: 10.1002/chem.200801103.
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 C8-C14 bond in a stereoselective fashion. The allene which results from this sequence then enables a second critical carbon-carbon 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.
我们通过一种高度汇聚的方法全面描述了强效昆虫拒食剂印楝素的首次合成。采用O-烷基化反应将十氢化萘酮和炔丙基甲磺酸酯片段结合在一起，之后克莱森重排以立体选择性方式构建中心C8-C14键。该序列产生的丙二烯随后引发第二个关键的碳-碳键形成事件，借此通过5-外环自由基环化过程生成天然产物中存在的[3.2.1]双环体系。最后，利用我们早期对该天然产物反应性研究获得的知识，一系列精心设计的步骤完成了这个具有挑战性分子的合成。
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