A general, asymmetric, and noniterative synthesis of trideoxypropionates. Straightforward syntheses of the pheromones (+)-vittatalactone and (+)-norvittatalactone.
A general, asymmetric, and noniterative synthesis of trideoxypropionates. Straightforward syntheses of the pheromones (+)-vittatalactone and (+)-norvittatalactone.
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DOI：
10.1021/jo202330b
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发表时间：
2012-01
期刊：
影响因子：
--
通讯作者：
C. Weise;Matthias C Pischl;A. Pfaltz;C. Schneider
中科院分区：
文献类型：
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作者：
C. Weise;Matthias C Pischl;A. Pfaltz;C. Schneider
开发了一种新颖的、高度立体控制的、非常灵活的光学纯形式的生物学相关三脱氧丙酸酯结构单元的合成方法。通过热氧-Cope重排、铱催化氢化和烯醇化物甲基化三步反应，以高产率合成了相对构型可调的三脱氧丙酸酯。此外，官能化的端基允许化学选择性操作和链的进一步延长。基本的策略构成了第一个非迭代过程的组装聚脱氧丙酸酯，并已进一步应用于信息素（+）-vittatalactone和（+）-norvittatalactone的全合成，这已被分离出的条纹黄瓜甲虫Acalymma vittatum。
A novel, highly stereocontrolled, and very flexible synthetic access to biologically relevant trideoxypropionate building blocks in optically pure form has been developed. On the basis of a three-step sequence comprising a thermal oxy-Cope rearrangement, an iridium-catalyzed hydrogenation, and an auxiliary-controlled enolate methylation, trideoxypropionates with easily adjustable relative configuration were synthesized in excellent yields. In addition, the functionalized end groups allow for chemoselective manipulations and further elongation of the chain. The underlying strategy constitutes the first noniterative process for the assembly of polydeoxypropionates and has further been applied in total syntheses of the pheromones (+)-vittatalactone and (+)-norvittatalactone, which had been isolated from the striped cucumber beetle Acalymma vittatum.