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Construction of the Isocopalane Skeleton: Application of a Desulfinylative 1,7-Hydrogen Atom Transfer Strategy

机译:异铜烷骨架的构建:脱硫酰化的1,7-氢原子转移策略的应用

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摘要

Two attractive chirons, aldehyde 6 and chloride 7, exhibiting functionalized ent-spongiane-type tricyclic skeletons (ABC ring system), have been constructed and their absolute configurations have been studied by NMR spectroscopy and confirmed by single-crystal X-ray diffraction. Both of these chirons are derived from commercially available andrographolide in good yield. Aldehyde 6 is obtained through a novel K2S2O8-catalyzed aquatic ring-closing reaction of allylic sodium sulfonate and intramolecular 1,7-hydrogen atom transfer process. Further mechanistic investigations demonstrate that the 1,7-hydrogen atom transfer is a free-radical process, whereby hydrogen migrates from C18 to C17, as evidenced by double-18- deuterium-labeled isotope experiments. Prospective applications of these two chiral sources are also discussed.
机译:构造了两个有吸引力的丁二醛,分别是醛化6和氯化物7,它们具有官能化的对偶-海绵型三环骨架(ABC环系统),并且它们的绝对构型已通过NMR光谱研究,并通过单晶X射线衍射得以证实。这两种Chiron均以良好的产率衍生自市售穿心莲内酯。通过新型的K2S2O8催化的烯丙基磺酸钠的水生闭环反应和分子内1,7-氢原子转移过程获得醛6。进一步的机械研究表明,1,7-氢原子转移是一个自由基过程,氢由此从C18迁移到C17,双18氘标记的同位素实验证明了这一点。还讨论了这两种手性来源的预期应用。

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