The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Org Lett. 2012 Sep 7;14(17):4354-7. doi: 10.1021/ol3017963. Epub 2012 Aug 14.
Synthetic efforts toward the chlorinated aza-propellane alkaloid acutumine (1) are described. The key vicinal quaternary centers were constructed by a photochemical [2 + 2] cycloaddition reaction of a furanyl-tetrahydroindolone. Dihydroxylation of the [2 + 2] product enabled a tandem retro-aldol/intramolecular ketalization reaction, which revealed the aza-propellane core of 1 while generating an unusual, caged, pentacyclic hemiketal product.
描述了对氯化氮杂推进烷生物碱 acutumine(1)的合成研究。关键的偕四元季碳中心是通过呋喃基-四氢吲哚酮的光化学[2+2]环加成反应构建的。[2+2]产物的二羟基化使串联的反醛缩/分子内缩酮化反应成为可能,这不仅揭示了 1 的氮杂推进烷核心,同时还生成了一种不寻常的、笼状的、五环半缩酮产物。