Zhuo Junming, Zhu Chunlin, Wu Jinbao, Li Zijian, Li Chao
Graduate School of Peking Union Medical College and Chinese Academy of Medical Sciences, Beijing 100730, China.
National Institute of Biological Sciences, Beijing 102206, China.
J Am Chem Soc. 2022 Jan 12;144(1):99-105. doi: 10.1021/jacs.1c11623. Epub 2021 Dec 27.
Here we report a general [3 + 2] radical annulation that allows the facile construction of bicyclo[3.2.1]octane motifs in -kaurane- and beyerane-type diterpenoids. This radical annulation is difficult to control but was realized by harnessing an unprecedented and counterintuitive effect of TEMPO. Eleven natural products with a wide array of oxidation states are easily prepared, demonstrating the powerful utility of this straightforward synthetic strategy.
在此，我们报道了一种通用的[3 + 2]自由基环化反应，该反应能够在贝壳杉烷型和贝叶烷型二萜类化合物中轻松构建双环[3.2.1]辛烷结构单元。这种自由基环化反应难以控制，但通过利用TEMPO一种前所未有的、违反直觉的效应得以实现。轻松制备了11种具有多种氧化态的天然产物，证明了这种直接合成策略的强大效用。
