通过氧拼接策略四步合成抗疟豆蔻过氧化物。

Hu Xirui, Maimone Thomas J

Department of Chemistry, University of California , Berkeley, California 94720, United States.

J Am Chem Soc. 2014 Apr 9;136(14):5287-90. doi: 10.1021/ja502208z. Epub 2014 Mar 27.

A four-step synthesis of the antimalarial terpene cardamom peroxide, a 1,2-dioxepane-containing natural product, is reported from (-)-myrtenal and molecular oxygen. This highly concise route was guided by biosynthetic logic and enabled by an unusual manganese-catalyzed, tandem hydroperoxidation reaction. The absolute configuration of the cardamom peroxide is reported, and its mode of fragmentation following Fe(II)-mediated endoperoxide reduction is established. These studies reveal the generation of reactive intermediates distinct from previously studied endoperoxide natural products.

报道了一种从（-）-桃金娘烯醛和分子氧出发，分四步合成抗疟萜类化合物豆蔻过氧化物（一种含1,2-二氧杂环庚烷的天然产物）的方法。这条高度简洁的路线以生物合成逻辑为指导，并通过一种不寻常的锰催化串联氢过氧化反应得以实现。报道了豆蔻过氧化物的绝对构型，并确定了其在Fe（II）介导的内过氧化物还原后的裂解模式。这些研究揭示了不同于先前研究的内过氧化物天然产物的反应性中间体的生成。