倍半萜chloranthalactone A和F的全合成

趙剛

摘要：采用仿生生源合成策略，金粟蘭內(nèi)酯（+）-chloranthalactone F被首次合成。探索了如何構(gòu)建（+）-chloranthalactone F 的生源前體3/5/6三環(huán)不飽和內(nèi)酯（+）-chloranthalactone A。從（R）-Hajos-Wiechert酮出發(fā)，選擇性合成了熱力學不穩(wěn)定的反式氫化茚酮，經(jīng)Wharton 轉(zhuǎn)化和 Simmons-Smith環(huán)丙烷化等關(guān)鍵步驟，制備了3/5/6三環(huán)不飽和內(nèi)酯（+）-chloranthalactone A，最終經(jīng)[2+2]仿生途經(jīng)完成了首次（+）-chloranthalactone F全合成。該工作揭示了（+）-chloranthalactone F的生源合成途徑以及確定其絕對構(gòu)型。

關(guān)鍵詞：全合成；倍半萜；chloranthalactone A； chloranthalactone F

Total synthesis of sesquiterpenoid chloranthalactone A and F

Abstract：Total synthesis of （+）-chloranthalactone F was first been accomplished via biomimetic synthetic strategies. Firstly， the synthetic strategies to the unsaturated lactones and the construction of the 3/5/6 tricyclic framework were probed into the biomimetic monomer named （+）-chloranthalactone A. Starting from the prepared （R）-Hajos-Wiechert ketone， a trans-fused， thermodynamically unstable hydrindanone was synthesized and further exploration ensured the asymmetric synthesis of congested 3/5/6 core skeleton by way of Wharton transposition and Simmons-Smith reaction. Subsequently， the syntheses of unsaturated lactones were accomplished basing on the strategies of ketone transposition and [2+2] electro-cyclization/ring-opening/lactonization. This work has revealed biogenesis pathway of （+）-chloranthalactone F and to determine its absolute configuration.

Keywords：Total synthesis； sesquiterpenoid； chloranthalactone A； chloranthalactone F

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