通过自由基框架重构合成 Swinhoeisterol A、Dankasterone A 和 B 以及 Periconiastone A。
Synthesis of Swinhoeisterol A, Dankasterone A and B, and Periconiastone A by Radical Framework Reconstruction.
机构信息
Institute of Chemistry and Biochemistry , Freie Universität Berlin , Takustraße 3 , 14195 Berlin , Germany.
出版信息
J Am Chem Soc. 2020 Jan 8;142(1):104-108. doi: 10.1021/jacs.9b12899. Epub 2019 Dec 27.
A switchable radical framework reconstruction approach to structurally unique 13(14 → 8),14(8 → 7)di-steroid swinhoeisterol A was developed. The conversion of an ergostane skeleton proceeded through the intermediacy of a 13(14 → 8)-framework as present in the dankasterone and periconiastone family of natural products and features a β scission of a 14-alkoxy radical with concomitant generation of the C8-C13 bond. From this intermediate, and dependent on the conditions employed, the cascade continues with a Dowd-Beckwith rearrangement and leads to the formation of the 13(14 → 8),14(8 → 7)di-framework of the swinhoeisterol class of natural products. The synthesis of these frameworks then allowed for efficient access to swinhoeisterol A (), dankasterone A (Δ-), dankasterone B (), and periconiastone A ().
开发了一种可切换的自由基框架重构方法，用于结构独特的 13(14→8),14(8→7)二-甾族化合物 swinhoeisterol A。麦角甾烷骨架的转化通过 13(14→8)-框架中间体进行，该中间体存在于 dankasterone 和 periconiastone 天然产物家族中，具有 14-烷氧基自由基的β断裂，同时生成 C8-C13 键。从中介体开始，并取决于所采用的条件，级联反应继续进行 Dowd-Beckwith 重排，导致 swinhoeisterol 类天然产物的 13(14→8),14(8→7)双框架的形成。这些框架的合成然后可以有效地获得 swinhoeisterol A()、dankasterone A(Δ-)、dankasterone B()和 periconiastone A()。
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