Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Japan.
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.
Org Lett. 2022 Nov 4;24(43):7939-7943. doi: 10.1021/acs.orglett.2c03068. Epub 2022 Oct 21.
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.
一种新的合成策略，通过阴离子 8π 电环反应形成一个七元碳环，促进了第一个全合成 6,11-环氧异杜松烷天然倍半萜的 10 步反应，最长线性序列的产率为 9.0%。通过合成提议的结构及其 C6 差向异构体，纠正了错误指定的提议立体化学。此外，通过从环氧腈中串联脱氰/五元环形成，简洁地构建了 5-7 稠合环系统。
