可见光照光氧化还原催化实现了拟生源尼因定 A、B、D 和 Rasumatranin D 的仿生合成。
Visible-Light Photoredox Catalysis Enables the Biomimetic Synthesis of Nyingchinoids A, B, and D, and Rasumatranin D.
机构信息
Department of Chemistry, The University of Adelaide, Adelaide, SA 5005, Australia.
出版信息
Angew Chem Int Ed Engl. 2019 Feb 25;58(9):2791-2794. doi: 10.1002/anie.201814089. Epub 2019 Feb 4.
The total synthesis of nyingchinoids A and B has been achieved through successive rearrangements of a 1,2-dioxane intermediate that was assembled using a visible-light photoredox-catalysed aerobic [2+2+2] cycloaddition. Nyingchinoid D was synthesised with a competing [2+2] cycloaddition. Based on NMR data and biosynthetic speculation, we proposed a structure revision of the related natural product rasumatranin D, which was confirmed through total synthesis. Under photoredox conditions, we observed the conversion of a cyclobutane into a 1,2-dioxane through retro-[2+2] cycloaddition followed by aerobic [2+2+2] cycloaddition.
通过连续重排使用可见光光氧化还原催化有氧[2+2+2]环加成组装的 1,2-二氧杂环己烷中间体，实现了 nyingchinoids A 和 B 的全合成。通过竞争[2+2]环加成合成了 nyingchinoid D。根据 NMR 数据和生物合成推测，我们提出了相关天然产物 rasumatranin D 的结构修订，通过全合成得到了证实。在光氧化还原条件下，我们观察到通过反-[2+2]环加成将环丁烷转化为 1,2-二氧杂环己烷，然后进行有氧[2+2+2]环加成。
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