Total synthesis of (±)-cafestol: a late-stage construction of the furan ring inspired by a biosynthesis strategy.
Total synthesis of (±)-cafestol: a late-stage construction of the furan ring inspired by a biosynthesis strategy.
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DOI：
10.1021/ol500623w
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发表时间：
2014-04
期刊：
影响因子：
5.2
通讯作者：
Lili Zhu;Jisheng Luo;R. Hong
中科院分区：
文献类型：
--
作者：
Lili Zhu;Jisheng Luo;R. Hong
一种有效的生物启发的方法来全合成（±）-呋喃的特点是后期安装呋喃环与温和的Au催化的环异构化。Et 2AlCl促进的双烯环化和随后的Friedel-Crafts反应提供了具有高立体选择性和区域选择性的克级三环体系。此外，一个高度立体选择性的SmI 2介导的贝壳杉烯-烯烃自由基环化取代的关键双环[3.2.1]辛烷骨架，提供了一个先进的中间体，用于合成其他含氧对映贝壳杉烯二萜。
An efficient bioinspired approach to the total synthesis of (±)-cafestol features a late-stage installation of the furan ring with a mild Au-catalyzed cycloisomerization. The Et2AlCl-promoted aldehyde-ene cyclization and subsequent Friedel-Crafts reaction deliver a requisite tricyclic system in gram scale with high stereo- and regioselectivity. Moreover, a highly stereoselective SmI2-mediated aldehyde-alkene radical cyclization furnishes the key bicyclo[3.2.1]octane skeleton to offer an advanced intermediate for the synthesis of other oxygenated ent-kaurene diterpenoids.