Total Synthesis and Structural Revision of the 6,11-Epoxyisodaucane Natural Sesquiterpene Using an Anionic 8π Electrocyclic Reaction
Total Synthesis and Structural Revision of the 6,11-Epoxyisodaucane Natural Sesquiterpene Using an Anionic 8π Electrocyclic Reaction
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DOI：
10.1021/acs.orglett.2c03068
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发表时间：
2022-10-21
期刊：
影响因子：
5.2
通讯作者：
Tanino，Keiji
中科院分区：
文献类型：
--
作者：
Kato，Ranmaru;Saito，Hiroki;Tanino，Keiji
采用阴离子8π电环化反应形成7元碳环的新合成策略，首次以9.0%的产率在最长的线性序列中完成了6，11-环氧异十二烷天然倍半萜的全合成。错误分配的建议立体化学通过合成建议的结构及其C6差向异构体进行校正。此外，5-7-稠环系统是通过串联脱氰/五元环形成从环氧腈简洁地构建。
A new synthetic strategy that forms a seven-membered carbocycle using an anionic 8π electrocyclic reaction facilitated the first total synthesis of the 6,11-epoxyisodaucane natural sesquiterpene in 9.0% yield over 10 steps in the longest linear sequence. The misassigned proposed stereochemistry was corrected by the synthesis of both the proposed structure and its C6 epimer. In addition, the 5-7-fused ring system was concisely constructed by tandem decyanation/five-membered-ring formation from an epoxynitrile.